JP2011042912A - Method for producing colored fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a colored fiber having a soft texture, providing coloration with a high color developing density without environmental problems, and having excellent level dyeing properties, clearness, sharpness, and fastness. <P>SOLUTION: There is provided the method for producing the colored fiber using a pigment. In the method, a coloring composition comprising a pigment dispersion and a cross-linking agent wet dispersed so as to have an average particle diameter within the range of 0.1-0.5 μm with a polymer type dispersing agent comprising a hydrophobic group-containing monomer and an ionic group-containing monomer as constituent components is diluted with a terpeneless reducer to provide a coloring ink. The resultant coloring ink is then printed on the fiber with a high-mesh screen plate of 150-350 meshes/inch. Heat treatment is subsequently applied to the printed fiber thereby cause a cross-linking reaction between the ionic groups of the polymer type dispersing agent and the cross-linking agent. As a result, the pigment is fixed on the fiber. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a colored fiber by screen-printing a composition containing a pigment as a colorant on a fiber using a high-mesh screen plate.

Conventionally, either a dye or a pigment is used for coloring a fiber. Coloring with dyes is a dye (colorant) having a different structure depending on the fiber type, that is, reactive dyes or direct dyes for cellulose fibers such as cotton and hemp, acid dyes for animal fibers such as wool and silk, and nylon fibers. Is an acid dye or disperse dye, a disperse dye is used for polyester fiber, and a cationic dye is used for acrylic fiber. These dyes are selected according to the fiber type and dyed by various dyeing methods.
However, coloring with dyes is a dyeing and dyeing method in which a dye is heated (absorbed) on a fiber in a large amount of water, washed with water and dried, a padding method in which the fiber is padded, steamed, washed with water, and dried. The dye can be mixed with the printing paste and printed with a flat screen plate, rotary screen plate or roller printing plate, and then the fiber can be colored by steaming, washing with water and drying, but steaming, washing and soaping, drying Since a process is required, the dyeing method is complicated and requires a considerable amount of energy. In addition, a large amount of waste liquid is generated by washing and soaping, which causes environmental problems. On the other hand, fibers colored with dyes are preferred as clothing because they are excellent in leveling properties, become deep colored products with high color density, have a soft texture, and are excellent in water absorption.
The printing process is performed by blending a dye with a water-soluble paste as a printing paste. However, since a fixing resin is not required like a pigment, a high mesh screen plate can be used. However, even with this printing method, it is not perfect to obtain a colored product with a delicate pattern. Even when a high mesh screen plate is used in the printing of synthetic fibers, bleeding (bleed) occurs, and the delicate pattern is printed. There is a problem in expressing, and in order to express the drawing sharply, it has been printed using a dye-resisting method.

On the other hand, coloring with a pigment is performed by mixing a pigment as a colorant and a water-soluble anionic or nonionic surfactant having a hydrophilic group and a lipophilic group as a dispersant in water, followed by glass beads and zirconia beads. , Titania beads, stainless spheres, etc., are wet dispersed in a mill to make a colorant, and the colorant is colored by a padding method together with a pigment fixing emulsion resin, or mixed with a reducer and an emulsion resin for fixing, and flat screen printing. In this method, a rotary screen printing or roller printing is performed and the pattern is colored on the fiber by drying.
The coloring method with pigments does not require the selection of a colorant depending on the fiber type compared to the coloring method with dyes, the processing method is simple, and the steaming, washing and soaping steps are not required. This is a safe processing method that is excellent in terms of environment since it does not cost and waste liquid does not occur.
However, in the processing method using pigment, in order to maintain fastness such as washing fastness, an emulsion resin for fixing the pigment must be blended, and as the color becomes darker, a larger amount of resin is required and the texture becomes harder. In addition, it has a problem that is difficult to obtain a soft and high-concentration colored product, and also has a problem of inhibiting the water absorption of the colored fiber because a large amount of the fixing emulsion is used.
Also, the conventional textile printing method using a pigment has a problem in continuous textile printing because the emulsion resin for fixing the pigment has a water-insoluble film stretched by drying during processing, causing clogging.
Therefore, the conventional pigment printing is printed using a low mesh screen plate of 50 to 120 mesh / inch, but because of this, the texture is hard and a sharp and delicate design cannot be printed. Due to the large amount, mold scumming occurred during continuous printing, resulting in problems such as poor leveling and unevenness on the printing surface, and unclear hue, and as a result, quality was inferior compared to colored products with dyes.
In addition, on the work surface during processing, the emulsion resin dries due to volatilization of water, and soils the machine during padding, contamination of the dried film during coating and soils the machine, clogging of the plate during screen printing, There are problems such as filming or thickening of the colored pigment ink.

As what is related to coloring with such a pigment, for example, a pigment composed of a pigment composition having an average particle diameter of 200 nm or less and a binder polymer particle is known (Patent Document 1).
The above-mentioned known methods use finer pigment particles and binder polymer particles to thin the colored coating layer, maintain and improve the texture of the fiber structure, suppress voids in the coating layer, and fastness However, since this method uses fine particles as pigment particles, it is necessary to devise measures such as prevention of re-aggregation during coloring processing and refinement means. It is hard to say that it is a simple method.
In addition, regarding a colorant using a pigment, an aqueous colorant characterized by containing a water-soluble polymer having a crosslinkable functional group and a pigment finely dispersed thereby (Patent Document 2), or a patent Claims 1. It is composed of 2.5 to 20% by weight of a carboxy group-containing polymerizable monomer, 1 to 10% by weight of a crosslinkable functional group-containing polymerizable monomer and 96.5 to 70% by weight of another polymerizable monomer. Soap comprising polymer thickened aqueous emulsion, printing paste (1) mixed with alkaline substance and hydrophobic organic compound, aqueous processed pigment (2) and crosslinkable organic compound (3) having two or more functional groups 1. Free coloring textile paste composition, and claims Aqueous processed pigment (2) is a carboxy group-containing polymerizable monomer 2.5 to 30 wt%, a crosslinkable functional group-containing polymerizable monomer 0 to 10 wt% and another polymerizable monomer 97.5. The composition according to claim 1 (cited document 3), which is an aqueous processed pigment mixed with an alkali-soluble polymer composed of ˜60% by weight.
However, since the above-described one uses a large amount of the fixing polymer, it is expected that the above-mentioned problems in continuous printing processing, that is, problems such as clogging of the plate and film coating will occur.
Next, in order to permeate the printed ink into the fiber, or to increase the leveling and color density, the reducer is usually printed using a terpene reducer containing a terpene. The ink containing the solvent has a concern of deteriorating the environment due to the VOC problem.
A method of printing using a turpentless reducer that does not contain a terpen has been developed. However, there are problems such as poor penetrability, leveling, color density, and unclear coloration.
From the above, there are no environmental problems, excellent leveling, sharpness, sharpness, penetrability, deep coloration with high color density, and coloring with pigments that are soft and have excellent fastness The development of fiber is awaited.

JP 2006-299018 A JP 2004-201877 A Japanese Patent Publication No.57-89680

  An object of the present invention is to provide a method for producing a colored fiber having a soft texture, no environmental problems, high color density, and excellent levelness, sharpness, sharpness, and fastness. There is.

The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems. As a result, the pigment is composed of a hydrophobic group-containing monomer and an ionic group-containing monomer as components in color printing of fibers with pigments. A high-mesh screen is formed on a fiber by blending a colored composition in which a cross-linking agent is blended with a pigment dispersion wet-dispersed in a polymer type dispersant with an average particle diameter in the range of 0.1 to 0.5 μm into a terpenless reducer. By printing using a plate and applying heat treatment, a crosslinking reaction occurs between the ionic group of the polymeric dispersant and the crosslinking agent at the time of coloring, and it is excellent in leveling, sharpness, sharpness, Knowing that colored fibers with a soft feel, breathability and excellent water absorption can be obtained, and if necessary, pigment dispersion can be used in combination with a polymeric dispersant and a dispersion aid in combination with a specific surfactant. By using the pigment dispersion during long-term storage It can have learned to be stabilized.
In addition, by blending the pigment dispersion into a turpentless reducer and printing with a high mesh screen plate, there is no mold scum during continuous printing (the back of the mold does not adhere), and there is no unevenness on the printing surface. In addition, it is known that it becomes a colored product with a high color density and the permeability to fibers is improved, and in addition, the core-shell type water-based resin and emulsion resin are blended as a minimum as a pigment fixing aid, and there is a problem in workability. As a result of further research, the present invention has been completed.
That is, according to the present invention, in the textile printing with pigments, by using the above-mentioned coloring composition, it is possible to perform pigment printing with a high mesh screen plate. Knowing what is obtained, the present invention has been completed.

The present invention comprises the following inventions.
1. In the method for producing a colored fiber using a pigment, the average particle diameter is in the range of 0.1 to 0.5 μm by a polymer type dispersant having a hydrophobic group-containing monomer and an ionic group-containing monomer as constituent components. A coloring composition comprising a wet dispersion of a pigment dispersion and a crosslinking agent is diluted with a terpenless reducer to form a colored ink, and then the colored ink is applied to a fiber at a high mesh screen of 150 to 350 mesh / inch. A method for producing a colored fiber, wherein the pigment is fixed on the fiber by causing a crosslinking reaction between the ionic group of the polymer dispersant and the crosslinking agent by printing with a heat treatment and applying a heat treatment.
2. 2. The method for producing a colored fiber as described in 1 above, wherein the ionic group of the polymeric dispersant is a carboxyl group, a sulfonic acid group or a phosphoric acid group.
3. 3. The method for producing colored fibers according to 1 or 2 above, wherein the polymer dispersant has a weight average molecular weight in the range of 2,000 to 50,000 and an acid value in the range of 100 to 250.
4). A compound having an oxazoline group, an isocyanate group, an ethyleneimine group, an aziridine group, a carbodiimide group, or a silane coupling group, or a blocked isocyanate group that reacts after heating, where the crosslinking agent reacts at room temperature or low temperature, 4. The method for producing a colored fiber according to any one of 1 to 3 above, which is a compound having a hydrazide group or a diacetone acrylamide group.
5). The colored fiber according to any one of 1 to 4 above, wherein the wet dispersion uses a surfactant comprising polyoxyethylene aryl ether sulfate ester salt or polyoxyethylene alkyl ether sulfate ester salt as a dispersion aid. Manufacturing method.
6). 6. The method for producing a colored fiber according to any one of 1 to 5 above, wherein the terpenless reducer is a blend of a cross-linked acrylic resin as a thickener.
7). 7. The method for producing a colored fiber according to any one of 1 to 6 above, wherein the crosslinking reaction is performed using a core-shell type aqueous resin as a fixing aid.
8). The above fixing assistant is a core-shell type aqueous resin in which the shell component is a water-soluble acrylic ester resin, a copolymer resin containing urethane ester or a urethane resin, and the core component is a resin obtained by polymerizing a hydrophobic vinyl monomer. 8. A method for producing a colored fiber according to 7.
9. By using a terpeneless reducer in which the cross-linking reaction is blended in the range of 0.1 to 10 parts, preferably 0.1 to 6 parts, of a core-shell type aqueous resin with respect to 1 part of the pigment as a fixing aid, 9. The method for producing a colored fiber according to 7 or 8, wherein a crosslinking reaction is caused to occur between the polymer-type dispersant, the core-shell type aqueous resin and the crosslinking agent.
10. 10. The method for producing colored fibers according to any one of 1 to 9 above, wherein the softening agent comprising silicone oil is blended in the colored ink or used as a post-treatment of the colored fibers.
11. 11. A method for producing colored fibers, wherein the colored fibers obtained by the method for producing colored fibers according to any one of 1 to 10 above are further padded with silicone oil.
12 A colored fiber obtained by the method for producing a colored fiber according to any one of 1 to 10 above, wherein the colored fiber is a natural fiber, a semi-synthetic fiber, a synthetic fiber, or a blend thereof.

The present invention has been completed based on the following findings.
1. Problems of the prior art Printing using a conventional pigment as a colorant is a non-ionic surfactant or an aqueous pigment dispersion using an anionic surfactant as a colorant, and usually uses a turpentine. Contains a reducer, wetting agent, surfactant, and a large amount of emulsion resin as a fixing agent, and after inking, a pattern is formed on the fiber using a screen plate of 50 to 120 mesh / inch The textile printing method was performed.
The flat screen plate is a woven yarn of polyester or nylon, whereas the rotary screen plate is a plate in which holes of various meshes are formed in a stainless plate having a thickness of 90 to 120 μm.
However, the above screen printing method has the following problems.
(Problem 1)
Conventional pigment dispersants use nonionic surfactants or anionic surfactants, but these surfactants inhibit pigment fixation due to poor affinity with fibers during coloring. In addition, the surfactant remaining in the fiber is water-soluble, which deteriorates the washing fastness and friction fastness of the colored fiber.
For this reason, conventionally, a large amount of emulsion resin has been blended in the colored ink as a fixing agent in order to fix the pigment onto the fiber with high fastness.
However, the emulsion resin can firmly adhere the pigment to the fiber, but on the other hand, it forms a water-insoluble film when it is dried. Could not be printed.
As a result, only a rough low-mesh screen plate of 50 to 120 mesh / inch could be used, the pattern was unclear, and printing that formed a clear and sharp pattern could not be performed.
In addition, since a low mesh screen plate is used, the coating amount is large, and ink adheres to and laminates on the back of the mold during continuous printing, resulting in a so-called mold squeeze phenomenon. Dyeability was not obtained.
Furthermore, when a large amount of emulsion resin is blended in order to obtain wash fastness and friction fastness, there is a problem of impairing the texture of the colored fiber and a problem of inhibiting water absorption. Therefore, in the textile printing method using a pigment, it is difficult to obtain colored fibers having a high texture and a high texture.
As a solution to the problem of workability due to the blending of a large amount of the above emulsion resin, measures have been taken to blend a large amount of wetting agent and delay drying. Therefore, the problem has not been solved.
Moreover, even if such a method is taken, clogging in printing using a high mesh screen plate has not been completely prevented.
Furthermore, the conventional textile printing method using a pigment contains a large amount of an emulsion resin for fixing in order to maintain fastness. The fixing agent is in the form of an emulsion and particles of 0.1 to 0.3 μm are contained. Forming.
That is, the pigment particles and the emulsion particles have substantially the same particle size, and after printing, both of them exist as independent particles in the fiber and penetrate at different speeds.
As a result, since the surfactant is bonded to the pigment surface, the penetrating power is strong, and in order to inhibit the surface color development and increase the color density, more pigment is added or the coating amount is increased with a low mesh. Other than to do, it was difficult.
Such an independent phenomenon is that the pigment and the fixing agent are fixed in the form of dots, so even if the fixing agent is fused and dried to be transparent, the color density of the pigment is slightly white due to the problem of the refractive index of light. It becomes turbid and impairs the sharpness of the colored material.
Therefore, a vivid colored fiber having a depth like a fiber colored with a dye cannot be obtained.
In addition, since the pigment and the fixing agent are considered to be fixed to the fiber in a tangled state, the fixing efficiency is poor and a large amount of the fixing agent to the pigment is required, which further hinders the texture of the colored fiber. It was.
Therefore, in order to maintain fastness with a high concentration of coloring, the amount of fixing agent must be increased, so that the colored fibers can only be obtained with a very hard texture, and the colored fibers can only have poor water absorption. It was not obtained.
(Problem 2)
Conventional reducers for pigment printing have been usually printed using a reducer containing a turpentine in order to allow the colored ink to penetrate into the fiber to produce a clear color or to soften the texture. Under recent environmental problems, inks containing organic solvents have been a problem that deteriorated the environment due to VOC problems.
Therefore, in recent years, a method of printing using a turpentless reducer that does not contain a turpent has been developed and performed. The reality is that it is widely used.

2. Solution It has been found that the above problem can be solved by the following solution.
(Solution 1) Colored composition comprising pigment dispersion and cross-linking agent As a colored composition, wet dispersion was performed using a polymeric dispersant containing a hydrophobic group-containing monomer and an ionic group-containing monomer as constituents. A combination of a pigment dispersion and a crosslinking agent is used.
That is, by using a crosslinking agent to crosslink the ionic group of the polymeric dispersant, the dispersant becomes water-insoluble, and further becomes a resin to form a large polymer, so that it functions as a pigment fixing agent. Will be demonstrated.
As a result, unlike conventional pigment dispersants, a large amount of emulsion resin is not required. Therefore, even if the pigment dispersion of the present invention is blended with a terpenless reducer and printed with a high mesh screen plate, continuous printing is performed. Colored fibers excellent in washing fastness and friction fastness can be obtained without clogging in the inside, and the texture of the obtained colored fibers is flexible and does not inhibit water absorption. Is obtained.
Further, by using a specific surfactant in combination as a dispersion aid, the dispersion stability can be further improved, and the long-term storage stability of the pigment dispersion can be improved.
As said crosslinking agent, it has reactivity at normal temperature or low temperature, oxazoline compound, isocyanate compound, epoxy compound, ethylene urea compound, ethyleneimine compound, aziridine compound, melamine compound, carbodiimide compound, silane coupling compound, reaction after heating A blocked isocyanate compound, an organic acid hydrazide compound, a diacetone acrylamide compound and the like can be used.
In this case, when a blocked isocyanate compound, an organic acid hydrazide compound, or a diacetone acrylamide compound that reacts after heating is used as a cross-linking agent, it is possible to make one color of colored ink, eliminating waste of colored ink, It is possible to save labor extremely economically.
As described above, the polymer dispersant of the present invention is a water-soluble dispersant, and the pigment and polymer are dispersed on the fiber by printing the pigment dispersion dispersed with the dispersant together with the crosslinking agent. The dispersant and cross-linking agent are integrated and printed in a state where the pigment is coated with the polymer dispersant. After that, heat treatment is applied to maintain the coating state and fix it. It will be a thing.
As a result, the present invention is advantageous in that the pigment can be fixed to the fiber with high fastness with the minimum necessary fixing agent.
(Solution 2) Colored ink diluted with a terpene-less reducer Pigment dispersion and cross-linking agent wet-dispersed with a polymeric dispersant containing the above hydrophobic group-containing monomer and ionic group-containing monomer as constituents The coloring composition consisting of is diluted with a terpenless reducer to form a colored ink, and then printed.
The preparation of the terpenless reducer in the case of using colored ink is performed by blending a thickener.
As a thickener, when a crosslinkable acrylic resin is used, the thickener component contains a functional group such as a carboxyl group remaining in the molecule, so that it can be crosslinked with a crosslinker. It is advantageous.
That is, the thickener component functions as a water-swellable thickening component in the color ink, and after printing, drying, and heat treatment, acts as a poorly water-soluble fixing component.
As a result, unlike thickeners using conventional terpene reducer non-ionic surfactants, it does not contain ingredients that impede fastness, so it retains fastness to washing and friction fastness even with a small amount of adhesive resin components. can do.
(Solution 3) Printing with a high mesh screen plate Coloring composition comprising a pigment dispersion wet-dispersed with a polymeric dispersant comprising a hydrophobic group-containing monomer and an ionic group-containing monomer as a constituent and a crosslinking agent The product is printed with a high mesh screen after being diluted with a turpentless reducer to obtain a colored ink.
By printing the colored ink of the present invention with a high-mesh screen plate, it is possible to obtain a sharp printed product having a clear color depth and excellent levelness.
Thus, when printing with a high mesh screen plate, there is no mold scum and excellent leveling.
Therefore, as in the past, problems have occurred in printing using a conventional pigment dispersion and a large amount of fixing emulsion resin by a turpentless reducer for printing, such as poor level uniformity, poor sharpness, and decreased color density. There is no problem.
In addition, the following Solution 4, Solution 5, and the like may be adopted.
(Solution 4) Fixing aid When the coloring composition is screen-printed with a high-mesh screen plate, an excellent colored fiber is obtained, but its fastness is inferior because of its small coating amount.
When a resin is blended as an adhering aid in order to increase the fastness, a conventional resin causes a problem of workability in a high mesh such as clogging, so that a large amount of resin cannot be blended.
Therefore, when a core shell type aqueous resin is used as a fixing aid, the fastness can be improved without causing clogging due to its re-dissolution property and without affecting the workability even if blended in a large amount.
That is, when a core-shell type aqueous resin is used as a fixing aid, a crosslinking reaction occurs between the polymer dispersant of the present invention and the crosslinking agent and between the core-shell type aqueous resin and the crosslinking agent at the time of coloring. The pigment can be firmly fixed on the fiber with the fixing resin.
In that case, the core-shell type water-based resin needs to be determined in consideration of texture, fastness, workability, and the like as a fixing aid. In other words, the smaller the texture and the better the fastness, the better. For example, 0.1 to 10 parts, preferably 0.1 to 6 parts, is added to 1 part of the pigment.
In addition, since the core-shell type water-based resin is a water-soluble resin with a shell portion that is water-soluble and a core portion that is hydrophobic, even if moisture evaporates on the screen plate during the printing process, the shell portion is water-soluble resin. It can be dissolved and can be continuously printed with a high mesh screen plate without clogging the screen plate.
As a result, it is possible to obtain a colored fabric having a soft texture that is inferior to the coloring by the dye and excellent in air permeability and water absorption.
As described above, the core-shell type water-based resin is water-soluble at the interface in contact with the pigment, so that the integration is not hindered in the colored ink, and the fixing function can be exhibited in a uniform state. In addition, it has become possible to solve the problems of color development, sharpness, texture, breathability, water absorption, workability, and fastness due to the fixing agent.
In addition, as a fixing aid, by adding an emulsion type aqueous resin in the range of 0.1 to 5 parts to 1 part of pigment, the fastness can be improved as in the case of the core-shell type aqueous resin. From the standpoint of integrating the fixing agent and the pigment, it is preferable to use the core-shell type aqueous resin as the fixing aid, and from the viewpoint of workability, color development, and sharpness, the core-shell type aqueous resin is used as the fixing aid. It is preferable to use it.
(Solution 5) Softener By padding the printed colored fiber with silicone oil, it becomes a colored fiber with a more excellent soft texture, and WAX, phthalate, which has been used as a softening agent. Compared to plasticizers such as acid esters and oil components such as mineral oil, the fiber surface is excellent in smoothness, friction fastness is improved, there is no tackiness, and a soft colored fiber with a smooth feel is obtained.

3. Effects of the Present Invention The present invention can achieve the following effects by adopting the above solution.
(1) Colored inks made of conventional pigments have been printed with 50-120 mesh / inch low-mesh screen plate using a large amount of fixing emulsion resin. It was the cause that hindered the texture more.
In addition, since a lot of colored ink is printed on the fiber, the so-called mold squeezing phenomenon occurs, in which the ink adheres to the back of the mold during wet-on-wet continuous printing, causing unevenness on the surface of the colored fiber, and leveling is a problem. It was.
However, if the colored fiber can be colored at a desired concentration, it is preferable from the economical and quality viewpoint that the amount of ink attached is small, and the pigment dispersed in the terpenless reducer of the present invention with a polymer dispersant, Colored inks using a cross-linking agent are printed with continuous inks that integrate each component. Therefore, even if printed with high mesh, the permeability to the fibers is constant and the fiber surface has the same efficiency. Since the pigment can be colored even at a high pigment concentration, it can be printed at a desired density with a high mesh and a minimum amount of ink.
That is, the amount of application on the surface of the printed material is small, and it has become possible to solve the problem of mold scum which has been a problem in the past during continuous printing.
In addition, since the fibers can be efficiently colored with the minimum required coating amount, even if synthetic fibers such as polyester are used, the ink can be printed without bleeding, so that a sharp colored fiber can be obtained.
For this reason, the anti-dyeing method used for coloring with dyes is not necessary, and it has become possible to print delicate designs by a labor-saving method.
Furthermore, by blending silicone oil with the turpentless reducer, the colored product can be softened, and further, the action of reducing the surface tension can occur, and the permeability can be further improved.
As a result, the smoothness of the colored product surface is improved and the friction fastness is also improved.
(2) Since the colored ink of the present invention is printed on a fiber with a continuous colored ink in which a water-swellable thickener, a pigment, a polymer dispersant, and a crosslinking agent are integrated, each component is The pigment penetrates into the fiber at a constant speed, and as a result, the pigment is colored on the fiber in a state of being coated with the cross-linking component, and a colored print having a wet color and vivid color and a high color density is obtained.
In addition, it is possible to obtain colored fibers that are inferior to those of dyed colored fibers, are soft to the touch, breathable, have excellent washing fastness and friction fastness, and require complex processes such as dye coloring processes. However, colored fibers can be obtained by an excellent processing method even in an environment that does not require energy.
(3) Dispersing the pigment with a polymer type dispersant having a hydrophobic group and an ionic group as essential components, or, if necessary, using a specific surfactant as a dispersion aid and dispersing the pigment. , And can be easily wet-dispersed in the range of 0.1 to 0.5 μm in average particle diameter, and by blending the dispersion with a crosslinking agent, after printing, drying and heat treatment, A cross-linking reaction occurs between the ionic group of the polymer dispersant and the cross-linking agent to fix the pigment on the fiber.
(4) By converting the pigment dispersion into a colored ink together with a terpenless reducer and a cross-linking agent, printing is performed with a high mesh screen plate in a state where the respective components are integrated. It is characterized in that a printed matter excellent in levelness, sharpness and sharpness can be obtained at a certain color density.
(5) The core-shell type aqueous resin is blended in the range of 0.1 to 10 parts, preferably 0.1 to 6 parts, and / or the emulsion type aqueous resin as pigment 1 as the fixing aid. The polymer dispersant and the cross-linking agent, and the core-shell type aqueous resin and the cross-linking agent are colored at the time of coloring by blending in the range of 0.1 to 5 parts with respect to the part, printing on the fiber, and drying and heat treatment. A crosslinking reaction occurs between the emulsion-type aqueous resin and the crosslinking agent, and the pigment is more firmly fixed on the fiber.
(6) Since the thickener component used in the terpenless reducer also undergoes printing, drying, and heat treatment steps, after the printing, drying and heat treatment is applied to the thickener component, any component will work efficiently after passing through the printing, drying, and heat treatment steps. In addition, it is possible to obtain a colored fiber having improved water resistance and excellent washing fastness and friction fastness without using a large amount of fixing resin such as a printing ink using a conventional pigment.
As a result, the fibers colored by the printing method of the present invention are soft in texture, excellent in breathability and water absorption, excellent in continuous printing workability, excellent in washing fastness, friction fastness, long-term ink stability, There is a special effect that it is excellent in any respect.
The colored ink for textile printing using the pigment of the present invention has two functions in the dispersant from the viewpoint that the polymer dispersant used as the pigment dispersant is cross-linked with a cross-linking agent and also used as a pigment fixing agent. Because it is not necessary to have a fixing agent, or the pigment can be firmly fixed on the fiber with a minimum amount of fixing aid, and each component is printed in an integrated state. It has become possible to obtain printed products with clear and deep color development, soft texture and excellent levelness.
By adopting these unprecedented rational means, it has become possible to produce high-quality colored fiber products as described above.
The above-mentioned excellent effects of the present invention are due to the above-mentioned solution. In particular, the use of a polymer type dispersing agent comprising a hydrophobic group-containing monomer and an ionic group-containing monomer as constituent components is used. It is brought about by the synergistic effect of adding a cross-linking agent and causing a cross-linking reaction with the ionic group of the polymeric dispersant, adding them to a nother pen reducer, and using a high mesh screen plate. The selection of the configuration of the present invention is particularly significant in view of the fact that the advantages of the present invention are excellent and the object of the present invention cannot be achieved without any of these.

Hereinafter, the present invention will be described in more detail.
The present invention provides a method for producing a colored fiber using a pigment, wherein (1) a polymer type dispersant having a hydrophobic group-containing monomer and an ionic group-containing monomer as a constituent component has an average particle size of 0.1. A coloring composition comprising a pigment dispersion wet-dispersed in a range of ˜0.5 μm and a crosslinking agent is diluted with a (2) terpenless reducer to obtain a coloring ink, and (3) the coloring ink is applied onto the fiber. Each step of printing with a high-mesh screen plate and (4) causing the crosslinking reaction between the ionic group of the polymer dispersant and the crosslinking agent by applying heat treatment to fix the pigment on the fiber. It is characterized in that it is an essential requirement.

"Manufacturing process"
The above steps (1) to (4) will be described in detail.
<Step (1): Colored composition>
The coloring composition is composed of the following pigment dispersion and a crosslinking agent.
1. Pigment Dispersion This pigment dispersion contains (A) a pigment and (B) a polymer-type dispersant as essential components, and (C) a dispersion aid as other components, and is then wet-dispersed in an aqueous medium. To prepare.
(A) Pigment It is necessary to use a pigment of the present invention having an average particle size of 0.1 to 0.5 μm, and if it deviates from this range, the intended purpose cannot be achieved.
As the pigment used in the pigment dispersion of the present invention, any pigment can be used as long as it can be used as a colorant for textiles, regardless of whether it is an organic pigment or an inorganic pigment.
For example, carbon black, iron oxide black pigment as black pigment, azo pigment as red pigment, quinacridone pigment, chromophthal pigment, diketopyrrolopyrrole pigment, anthraquinone pigment, azo pigment as yellow pigment Pigments, imidazolone pigments, titanium yellow pigments, indanthrene pigments as orange pigments, azo pigments, imidazolone pigments, blue, phthalocyanine pigments as green pigments, dioxazine pigments as violet pigments, quinacridone pigments A pigment such as titanium oxide, aluminum silicate, silicon oxide, or the like as a white pigment can be used, but is not necessarily limited thereto.
(B) Polymer Type Dispersant The polymer type dispersant comprises (a) a hydrophobic group-containing monomer and an ionic group-containing monomer as constituents, and the following (b) pigment: Those having characteristics such as dispersibility, (c) crosslinkability, (d) molecular weight, and (e) acid value are preferably used.
(A) Polymeric dispersant comprising a hydrophobic group-containing monomer and an ionic group-containing monomer as constituents As the polymeric dispersant, examples of the hydrophobic group-containing monomer include styrene monomer, phenyl Group-containing (meth) acrylates, (meth) acrylic acid alkyl esters, alkyl vinyl ethers, vinyl monomers such as (meth) acrylonitrile, polyisocyanates and polyols, or urethane group-containing vinyl monomers formed from polyamines Silicone formed from monomer, epoxy group-containing vinyl monomer formed from epichlorohydrin and bisphenol, ester group-containing vinyl monomer formed from monomers such as high carboxylic acid and polyalcohol, organosiloxane, etc. And group-containing vinyl monomers.
Examples of the ionic group-containing monomer include the following unsaturated carboxylic acid monomer, unsaturated phosphoric acid monomer, and anhydrides and salts thereof. ) Acrylic acid, methyl (meth) acrylic acid, crotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl ester of unsaturated dicarboxylic acid, phosphoric acid ester of hydroxyalkyl (meth) acrylate, (meth) Examples thereof include alkyl sulfonic acid acrylate.
In order to obtain a polymeric dispersant, these hydrophobic group-containing vinyl monomers and ionic group-containing monomers can be obtained by a copolymerization method, but other than the copolymerization method, for example, an ionic group It is also possible to employ a method such as urethane polymerization of a urethane-forming group-containing monomer into which is introduced in advance, and epoxy polymerization of an epoxy-forming group-containing monomer into which an ionic group has been introduced in advance. The polymer dispersant of the present invention can also be obtained by introducing a desired ionic group after polymerizing the basic polymer.
The polymeric dispersant of the present invention comprises a hydrophobic group-containing vinyl monomer and an ionic group-containing monomer as constituent components, but other components include, for example, hydroxyl groups and Monomers such as polyethylene oxide with amide groups, polyols, monomers containing hydroxyalkyl esters, acrylamide, hydroxyalkyl acrylate, vinyl acetate, vinyl alcohol, N-ethylmethacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, etc. Can be copolymerized.
(B) Pigment dispersibility Pigment fine particles adsorbed on the surface of the pigment and disperse (wet) with water at the time of pigment dispersion, and are ground by mechanical action to prevent re-aggregation of fine particles by electrostatic repulsion (repulsive force) or steric repulsion In addition, it has a function of suppressing sedimentation and suppressing thickening.
(C) Crosslinkability The polymeric dispersant has a function as a fixing agent because a crosslinking reaction occurs with an ionic group by the action of the crosslinking agent during coloring.
(D) Molecular weight The polymer type dispersant has an optimum molecular weight for the dispersion effect with respect to the pigment. When the molecular weight is increased beyond the molecular weight, the dispersion effect is low, the dispersion becomes high in viscosity, Causes aggregation. On the other hand, if the molecular weight is smaller than the optimum value, the effect as a fixing agent after crosslinking is low and water resistance and the like cannot be obtained.
Therefore, it is preferable to use a polymer dispersant having a weight average molecular weight of 2,000 to 50,000.
(E) Acid value The acid value of the polymer dispersant is different from that of the polymer dispersant by changing the copolymerization ratio of the hydrophobic group and the ionic group. The acid value of the molecular dispersant is preferably in the range of 100 to 250. When the acid value is higher than 250, water resistance cannot be obtained even if the crosslinking is performed by a crosslinking agent. When the acid value is lower than 100, the pigment dispersibility is poor, and pigment aggregation occurs during long-term storage. This is not preferable because of problems such as the above and an effect of inhibiting the integration with the pigment.
(F) Others The polymer dispersant can be used as water-soluble by adjusting pH with aqueous ammonia or the like, if necessary.
(C) Dispersing aid In addition to the above-mentioned polymer type dispersing agent, a surfactant can be used in combination as a dispersing aid.
As the dispersion aid, when the pigment is dispersed only with the polymer type dispersant, the separation action of the electric double layer occurs between the pigment and the polymer dispersant during long-term storage, that is, the desorption of the dispersant occurs, and the pigment aggregation In some cases, separation / sedimentation and thickening may occur. Therefore, in order to improve long-term storage stability, it is preferable to use a polymer dispersant and a surfactant as a dispersion aid in combination.
Any surfactant can be used as long as it is a surfactant, but an anionic surfactant can be preferably used.
Examples of the anionic surfactant include higher alcohol sulfates, higher alkyl ether sulfates, higher alcohol phosphates, alkylaryl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkyls. Examples thereof include ester phosphate ester salts, polyoxyalkylene aryl ether sulfate ester salts, polyoxyalkylene alkyl ether carboxylate salts, and polycarboxylate salts.
Among them, a preferable anionic surfactant is polyoxyethylene aryl ether sulfate salt or polyoxyethylene alkyl ether sulfate ester salt.
Among these, polyoxyethylene styryl phenyl ether sulfate ester salts are particularly preferable, and those having HLB of 10 to 18 are more preferable.
Examples of the counter cation as the salt of the anionic surfactant include alkali metals (for example, lithium, sodium, potassium and the like), ammonium and the like, and sodium or ammonium is preferable.

[Preparation of pigment dispersion]
The pigment dispersion is prepared by wet-dispersing (A) a pigment and (B) a polymer-type dispersant as other components together with (C) a dispersion aid in an aqueous medium as necessary. Can do.
1) Mixing ratio of pigment and polymer type dispersant The mixing ratio of pigment and polymer type dispersant should be in the range of 1.0: 0.1 to 2.0. The blending ratio (weight) when blending a specific surfactant as a dispersion aid used is 1.0: 0.1 to 2 for pigment: polymer dispersant: surfactant as a dispersion aid. 0.0: 0.1 to 0.3 is preferable. If it deviates from this range, problems such as ink density cannot be obtained, water resistance cannot be obtained, and washing fastness and friction fastness cannot be obtained.
2) Aqueous medium As the aqueous medium, water, a water-soluble organic solvent, or the like can be used. Examples of water-soluble organic solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, glycerin, Examples include diglycerin, 2-pyrrolidone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether.
3) Method for adjusting pigment dispersion The above (A) pigment, (B) polymer dispersant, if necessary, other components, and (C) the dispersion aid together with the above 2) aqueous medium, A pigment dispersion is obtained by wet dispersion with a mill-type disperser using glass beads, zirconia beads, titania beads, etc., and a high mesh screen plate with an average particle size in the range of 0.1 to 0.5 μm. Thus, a pigment dispersion having excellent printability can be obtained. That is, if it is smaller than 0.1 μm, it is inferior in hiding property, stability, light resistance, and heat resistance, and if it is larger than 0.5 μm, it is inferior in sharpness, the color density is low, and the components of the colored ink are integrated. It is not preferable because it causes problems such as deterioration of fastness due to inhibition, deterioration of sharpness, and clogging during printing.

2. Cross-linking agent This cross-linking agent reacts with the ionic group of the polymer-type dispersant to form a water-resistant polymer compound and to act as a pigment fixing agent.
As a crosslinking agent, a compound having an oxazoline group, an isocyanate group, an ethyleneimine group, an aziridine group, a carbodiimide group, or a silane coupling group that reacts at room temperature or low temperature, or a blocked isocyanate group that reacts after heating. , A compound having a hydrazide group or a diacetone acrylamide group can be used.
The above-mentioned latter can make the coloring composition into one liquid, is more efficient in terms of workability, and is economically suitable.

<Step (2): Colored ink>
The pigment dispersion of 1 can be blended with a fixing aid, a softening agent, etc., if necessary, diluted with a terpenless reducer to give a colored ink, and then subjected to the next colored ink printing step.
1. The terpenless reducer is usually prepared to have a viscosity required as a printing reducer.
Thickeners used for terpenless reducers include, for example, cross-linked acrylic resins such as water-swellable Alcoprint PTF and Alcoprint PTRV, water and, if necessary, alkali such as ammonia water to adjust the pH. Thus, a turpentless reducer having a viscosity necessary for a textile reducer can be obtained.
Such a thickener component is, after printing, dried and heat-treated by the action of a crosslinking agent, and then cross-linked, resulting in poor water solubility and improved water resistance, and does not impair washing fastness and friction fastness. Become.
In addition, the viscosity of the thickener component can be adjusted by using an associative urethane thickener or a surfactant as another rheology control agent.
The viscosity of the colored ink for textile printing is preferably 2000 to 50000 mPa · s, more preferably 5000 to 30000 mPa · s. Viscosity adjustment within this range can be easily controlled by adjusting the amount of thickener used in the terpenless reducer. When the viscosity is lower than 2000 mPa · s, the sharpness of the pattern when printed on the fiber is inferior, causing problems such as bleeding of ink on the fiber and poor printing workability. When the viscosity is higher than 50000 mPa · s, the permeability is deteriorated, and mold spreading due to accumulation of colored ink occurs on the fiber surface, so that the leveling property is deteriorated and the friction fastness is inhibited. Further, since the viscosity is high, there is a problem in continuous printability, and there are problems in leveling and sharpness.
2. Fixing aid Colored fibers with excellent fastness can be obtained without blending this fixing aid, but a fixing aid should be used in combination to improve washing fastness and friction fastness. Can do.
As a fixing aid, when a core-shell type aqueous resin is blended (0.1 to 10 parts, preferably 0.1 to 6 parts with respect to 1 part of the pigment), the ionic groups of the polymer dispersant and the crosslinking agent are used during coloring. At the same time, the cross-linking reaction occurs between the core-shell aqueous resin and the cross-linking agent, so that the pigment can be fixed on the fiber with the minimum amount of fixing agent, and printing using a high mesh screen plate However, it is possible to print a fine, clear and sharp pattern with good fastness without clogging the screen plate during continuous printing, and as a result, a colored fiber having a soft texture can be obtained. .
Examples of the core-shell type aqueous resin include water-soluble acrylate copolymer resins, acrylate ester / styrene copolymer resins, acrylate ester / methyl methacrylate having a carboxyl group, a sulfonic acid group, an amide group, a hydroxyl group, etc. at the terminal. A core-shell type aqueous resin obtained by polymerizing a hydrophobic vinyl monomer using an acrylate copolymer resin or a urethane resin as a shell and the water-soluble resin as a dispersant as a core component can be used. Examples include, but are not limited to, acrylate monomers, vinyl acetate monomers, urethane / (meth) acrylate monomers, vinyl chloride monomers, ethylene / vinyl acetate monomers, acrylonitrile monomers, and the like. Co-weight It is also possible to.
Further, if necessary, an emulsion type aqueous resin can be blended in the colored ink as a fixing aid in the range of 0.1 to 5 parts with respect to 1 part of the pigment. Sometimes, simultaneously with the reaction between the polymer dispersant and the cross-linking agent, a cross-linking reaction occurs to improve the fastness, and both fixing aids can be used in combination.
As the emulsion-type aqueous resin, a vinyl resin copolymer having a hydrophilic cross-linking group such as a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group at the molecular terminal is preferable. For example, an acrylate copolymer resin, a urethane resin, an acrylic resin / Urethane resin, acrylonitrile / acrylic acid ester copolymer resin, etc. can be used.
In addition, it is preferable to use the former core-shell type aqueous resin alone from the viewpoint of not inhibiting the integration of the components of the colored ink and not inhibiting the continuous printing workability.

3. Softening agent The following are used as the softening agent used for the colored ink of the present invention.
Silicone oils such as methylated silicone oil, amino silicone oil, carboxy-modified silicone oil, hydroxy-modified silicone oil, and epoxy group-modified silicone oil are suitable. That is, when these silicone oils are used as a softening agent, the effect of lowering the surface tension of the coloring composition occurs with the softening, and the permeability to the fibers is improved. As a result, the printed matter Can be printed smoothly, and a colored printed matter having excellent levelness can be obtained.

4). Other ingredients For improving the light resistance of colored inks, such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, urea, etc. as wetting agents to delay the drying of the ink, silicone oil, mineral oil, etc. as antifoaming agents Penetrants to improve fiber permeability, such as UV absorbers, antioxidants, ammonia water for pH adjustment, amines, organic acids, metal soaps, waxes, etc. to improve lubricity For example, a curing catalyst for promoting curing, a plasticizer for softening, and the like can be blended.

<Process 3: High mesh screen version>
The colored ink for printing is printed on the fiber using a high mesh screen plate, that is, a screen plate of 150 to 350 mesh / inch.
The printing machine is not particularly limited. That is, printing can be performed using a screen plate of 150 to 350 mesh / inch, and preferably, a screen plate of 180 to 300 mesh / inch is used for mold stencil, leveling, color density, sharpness, It is preferable in terms of sharpness.

<Step 4: Fixation of pigment on fiber by cross-linking reaction between polymer dispersant and cross-linking agent>
After printing with the above-described colored ink for printing on a high-mesh screen plate, the fixing of the pigment of the present invention onto the fiber causes a crosslinking reaction between the polymer dispersant and the crosslinking agent by applying heat treatment. Thus, the pigment is fixed on the fiber.
That is, in the present invention, after printing, each component is printed in an integrated state, and the polymer-type dispersant, the fixing aid, and the thickening component are cross-linked by a crosslinking agent, so that the fixing component can be more efficiently used. After drying, heat treatment is performed at 80 to 160 ° C. for 1 to 8 minutes. The texture is flexible, breathable, and absorbs water, has excellent color density, excellent leveling, and clearness. In addition, it is possible to form a pattern that is sharp and excellent in washing fastness and friction fastness on the fiber, and as a result, a colored fiber having a quality comparable to that of a dyed colored fiber is obtained.
However, when the crosslinking reaction proceeds by heat due to drying or when the crosslinking reaction proceeds by heat at about room temperature, normal heat treatment is not necessarily required. In the present invention, even in the case of such heat, the heat treatment is included.

"Fiber products"
By subjecting the fibers colored with the coloring composition of the present invention to a padding treatment with a treatment agent containing silicone oil, colored fibers with a softer texture can be obtained.
As the silicone oil, methylated silicone oil, aminosilicone oil, carboxy-modified silicone oil, hydroxy-modified silicone oil, and epoxy-modified silicone oil can be used. Among them, aminosilicone oil is most preferable as a softening effect.
The colored fiber by the high mesh screen plate using the colored ink of the present invention includes the following.
Examples of fiber types include synthetic fibers such as nylon, polyester, acrylic, and lactic acid fibers, semi-synthetic fibers such as acetate and rayon, natural fibers such as cotton, silk, hair, and hemp, and blended fibers, knitted fabrics, woven fabrics, and the like. Nonwoven fabrics, brushed fabrics and the like can be mentioned.
Examples of clothing include T-shirts, polo shirts, shirts, trainers, jerseys, pants, dresses, blouses, socks, shoes, scarves, handkerchiefs, and the like.
Examples of textile products other than clothing include bedding, sheets, curtains, car seats, sofas, car interiors, tents, bags, calendars, flags, bags, and decorations.

Colored fiber products printed using a high-mesh screen plate with colored inks using the coloring composition of the present invention have a high color density, excellent moldability without mold stencils, and a clear and sharp design that is fast to wash. The coloration of the present invention is excellent because it has excellent properties and friction fastness, has a soft texture, breathability, water absorption, and does not clog the screen plate during continuous printing. The textile printing method using the composition and the colored ink has a particularly high value.
Further, since the colored ink of the present invention does not contain a turpentine, it is also valuable in that no environmental problems occur.

Hereinafter, although an example is given and the present invention is explained still in detail, the present invention is not limited to these. The “parts” referred to in the examples and the like means “parts by weight” unless otherwise specified.
Example 1
<Preparation of pigment dispersion>
25 parts of a phthalocyanine-based blue pigment (CI Pigment Blue 15-3), a polymeric dispersant having a weight average molecular weight of 8,500 having a carboxyl group as an ionic group and a phenyl group as a hydrophobic group, and an acid value of 200 (solid 34 parts by weight, Johncrill 62: manufactured by BASF Japan Co., Ltd.) 25 parts, 5 parts of propylene glycol, 45 parts of water were mixed, and 2 hours in a bead mill (0.5 mm diameter glass beads, wet disperser). Dispersion was performed to obtain a blue pigment dispersion 1 having an average particle diameter of 0.248 μm.
The same procedure as in Blue Pigment Dispersion 1 was carried out except that the phthalocyanine blue pigment in Blue Pigment Dispersion 1 was replaced with an azo red pigment (CI Pigment Red 150). A red pigment having an average particle diameter of 0.292 μm Dispersion 2 was obtained.
<Tarpenless reducer adjustment>
96.25 parts of water, 1.25 parts of a cross-linked acrylic resin thickener (Alcoprint PTF: manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2 parts of propylene glycol were stirred and mixed uniformly to obtain a terpene-less reducer 1. It was.
<Adjustment of colored ink>
3 parts of the above blue pigment dispersion 1, 96 parts of the above terpenless reducer 1, 1 part of an antifoaming agent (SN deformer 777: manufactured by San Nopco), a blocked isocyanate crosslinking agent (Fixer N: Corporation) 3 parts of Matsui Dye Chemical Co., Ltd.) was blended to obtain a colored ink 1 for high mesh screen printing having a viscosity of 14,000 mPa · s.
Except that the blue pigment dispersion 1 of the coloring ink 1 was replaced with the red pigment dispersion 2, the same procedure was carried out as in the coloring ink to obtain a coloring ink 2 for high mesh screen printing having a viscosity of 15,000 mPa · s.
<Coloring method>
Using a screen pattern with a grid pattern of 250 mm / inch line width of 0.5 mm (horizontal) and colored ink 2 of 250 mesh / inch and a line width of 10 mm (vertical), the colored ink 1 is placed on a cotton broad. 1000m continuous printing using an auto screen printing machine, drying at 120 ° C with a dryer and heat treatment at 150 ° C for 3 minutes to produce blue (horizontal) and red (longitudinal) checkered colored fabric Obtained.
The obtained colored fabric had no change in the grid width after the start of printing and after 1000 m processing, and the 0.5 mm line was not cut off due to clogging.
Further, there was no mold block during continuous printing, no irritation occurred on the printing surface, and the leveling property was excellent.
Furthermore, the obtained quality is sharp and clear with no bleed, with a sharp pattern, soft texture, breathability and water absorption, and fastness to washing (JIS L-0217). 103 method (5 times) was grade 4 and the fastness to friction (JIS L-0849) was excellent in dry friction grade 2-3 and wet friction grade 2-3.

(Example 2)
<Coloring method>
The colored ink 1 used in Example 1 is a 180 mesh / inch line width 0.5 mm (horizontal) and the colored ink 2 is a 180 mesh / inch line width 10 mm (vertical) lattice-pattern rotary screen mold. A 1000m continuous printing is performed on a cotton loan using a rotary screen printing machine. After drying at 120 ° C with a dryer, heat treatment is performed at 140 ° C for 3 minutes to obtain a blue (horizontal) and red (vertical) lattice. A patterned fabric was obtained.
As in Example 1, the obtained colored fabric had no change in the lattice width after the start of printing and after 1000 m processing, and the 0.5 mm line was not cut due to clogging.
Further, there was no mold block during continuous printing, no irritation occurred on the printing surface, and the leveling property was excellent.
Furthermore, the obtained quality is sharp and clear with no bleed, with a sharp pattern, soft texture, breathability and water absorption, and fastness to washing (JIS L-0217). 103 method (5 times) was grade 4 and the fastness to friction (JIS L-0849) was excellent in dry friction grade 2-3 and wet friction grade 2-3.

(Example 3)
<Preparation of pigment dispersion>
25 parts of a phthalocyanine blue pigment (CI Pigment Blue 15: 3), a polymer type dispersant having a weight average molecular weight of 8,500 having an carboxyl group as an ionic group and a phenyl group as a hydrophobic group, and an acid value of 200 (solid 34 parts, Jonkrill 62: BASF Japan Ltd. 20 parts, anionic surfactant (polyoxyethylene styrenated phenyl ether ammonium sulfate, Haitenol NF13, Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts, propylene 3 parts of glycol and 47 parts of water were mixed and dispersed in a bead mill (0.6 mm diameter glass beads, wet disperser) for 2 hours to obtain 0.312 μm blue pigment dispersion 3.
Except that the blue pigment dispersion 3 of the blue ink 3 was replaced with an azo red pigment (CI Pigment Red 150), the same procedure was performed as for the pigment dispersion 3, and a red pigment dispersion 4 having an average particle size of 0.327 μm. Got.
<Tarpenless reducer adjustment>
94.5 parts of water, 3.0 parts of a cross-linked acrylic resin thickener (Alcoprint PTRV: manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2.5 parts of propylene glycol were stirred and mixed uniformly. Got.
<Adjustment of colored ink>
3 parts of the above blue pigment dispersion 3, 96 parts of the above terpenless reducer 2, 1 part of an antifoaming agent (SN deformer 777: manufactured by San Nopco), a blocked isocyanate crosslinking agent (Fixer N: Corporation) 3 parts of Matsui Dye Chemical Co., Ltd.) were blended to obtain a colored ink 3 for high mesh screen printing having a viscosity of 13,500 mPa · s.
Except that the blue pigment dispersion 3 of the coloring ink 3 was replaced with the red pigment dispersion 4, the same procedure was carried out as in the coloring ink 3 to obtain a coloring ink 4 for high mesh screen printing having a viscosity of 13,900 mPa · s.
<Coloring method>
The colored ink 3 is applied to a cotton knit using a screen pattern with a 300 mm / inch line width of 0.5 mm (horizontal) and the colored ink 4 of a 300 mesh / inch line width of 10 mm (vertical). 1000m continuous printing is performed using an auto screen printing machine, and after drying at 120 ° C with a dryer, heat treatment is performed at 140 ° C for 3 minutes to obtain blue (horizontal) and red (longitudinal) checkered colored fabrics. Obtained.
The obtained colored fabric had no change in the lattice width after the start of printing and after 1000 m processing, and the 0.5 mm line was not cut off due to clogging.
Further, there was no mold block during continuous printing, no irritation occurred on the printing surface, and the leveling property was excellent.
In addition, the quality obtained is sharp and clear with no bleed and the pattern of the lattice pattern is sharp and clear, the texture is sharp and clear, the texture is flexible and breathable In addition, there is water absorption, and in terms of fastness, washing fastness (JIS L-0217 103 method 5 times) is grade 4, dry fastness (JIS L-0849) is dry friction 2-3 grade, wet friction 2-3 grade And it was of excellent quality. In addition, a colored fabric excellent in permeability compared with Example 1 was obtained. In addition, when a surfactant was used in combination with the dispersion, the pigment dispersion was stable for a long period of time, and there was no increase in viscosity, separation or sedimentation even after one year.

Example 4
<Tarpenless reducer adjustment>
94.5 parts of water, 2.3 parts of a cross-linked acrylic resin thickener (Alcoprint PTRV: manufactured by Ciba Specialty Chemicals Co., Ltd.), a cross-linked acrylic resin thickener (Parabond 10N: Parachem Japan ( Co., Ltd.) 1.0 parts, 2.5 parts of propylene glycol, and 0.3 parts of 2% aqueous ammonia were stirred and mixed uniformly to obtain a terpeneless reducer 3.
<Adjustment of colored ink>
3 parts of blue pigment dispersion 1, 86 parts of terpenless reducer 3, core-shell type aqueous resin (water-soluble urethane resin having a carboxyl group at the end of the shell part, hydrophobic acrylic acid ester resin at the core part, solid content 45 parts: Rikabond SU200: Chuo Rika Kogyo Co., Ltd.) 8 parts, Antifoaming agent (SN deformer 777: San Nopco Co., Ltd.) 1 part, Aziridine type cross-linking agent (Fixer F: Matsui Pigment Chemical Co., Ltd.) 2 parts were blended to obtain a colored ink 5 for high mesh screen printing having a viscosity of 15,700 mPa · s.
Except that the blue pigment dispersion 1 of the colored ink 5 was replaced with the red pigment dispersion 2, the same procedure was carried out as in the colored ink 5 to obtain a colored ink 6 for high mesh screen printing having a viscosity of 16,000 mPa · s.
<Coloring method>
Using a screen pattern with a grid pattern of 180 mm / inch line width of 0.5 mm (horizontal) and colored ink 6 of 180 mesh / inch and a line width of 10 mm (vertical), the colored ink 5 is autoscreened on a polyester pond. 1000m continuous printing was performed using a printing machine, and after drying at 120 ° C with a dryer, heat treatment was performed at 150 ° C for 3 minutes to obtain a blue (horizontal) and red (longitudinal) checkered colored fabric. .
The obtained colored fabric had no change in the lattice width after the start of printing and after 1000 m processing, and the 0.5 mm line was not cut off due to clogging.
Further, there was no mold block during continuous printing, and no irritation was observed on the printing surface, and the leveling was excellent.
In addition, the quality obtained is sharp and clear with no bleed, and the pattern is sharp and clear. The quality obtained is sharp and clear, the texture is flexible, and the ventilation is good. Property, water absorption, fastness to washing (JIS L-0217 103 method 5 times) is 4-5 grade, fastness to friction (JIS L0849) is dry friction grade 4, wet friction 3-4 Grade and excellent quality.

(Example 5)
<Adjustment of colored ink>
Pre-emulsified silicone oil emulsion as softener (effective oil concentration 50 parts: Dyestone Printgen XA-1: Matsui Dye Chemical Co., Ltd.) 7 parts, Blue Pigment Dispersion 1 3 parts, Turpenless Reducer 3 78 parts, 5 parts of a core-shell type aqueous resin (water-soluble urethane resin having a shell-terminated carboxyl group, a core part is a hydrophobic acrylic ester resin and a solid content is 40 parts: Acryt WEM 3053: manufactured by Taisei Fine Chemical Co., Ltd.) 3 parts of emulsion-type aqueous resin having a carboxyl group as a cross-linking functional group (Rikabond ES620: manufactured by Chuo Rika Kogyo Co., Ltd .: solid content: 58 parts), 1 part of antifoaming agent (SN deformer 777: manufactured by San Nopco) , 3 parts of block isocyanate-based crosslinking agent (Fixer N: manufactured by Matsui Dye Chemical Co., Ltd.) To obtain a high mesh colored ink 7 for screen printing of viscosity 15,100mPa · s.
Except that the blue pigment dispersion 1 of the coloring ink 7 was replaced with the red pigment dispersion 2, the same procedure was performed as in the coloring ink 7 to obtain a coloring ink 8 for high mesh screen printing having a viscosity of 15,400 mPa · s.
<Coloring method>)
The above-mentioned colored ink 7 is made of nylon / polyurethane using a screen pattern of 180 mesh / inch line width 0.5 mm (horizontal) and colored ink 8 of 180 mesh / inch line width 10 mm (vertical). A 3000m continuous printing is carried out on a blended fabric using a rotary screen printing machine. After drying at 120 ° C with a dryer, heat treatment is performed at 150 ° C for 3 minutes to obtain a blue (horizontal) and red (longitudinal) lattice pattern. A colored fabric was obtained.
The obtained colored fabric had no change in the lattice width after the start of printing and processing of 3000 m, and the 0.5 mm line was not cut off due to clogging. Further, there was no mold block during continuous printing, and no irritation was observed on the printing surface, so that the leveling was excellent.
In addition, the obtained quality is sharp and clear with no bleed and the pattern of the lattice pattern is sharp, the texture is flexible, breathable, water-absorbing, and fastness to washing The properties (JIS L-0217 103 method, 5 times) were 4-5 grade, and the fastness to friction (JIS L-0849) was dry friction 4-5 grade and wet friction grade 4 grade.

(Example 6)
The colored fabric obtained in Example 5 was padded with a treatment liquid of 5 parts aminosilicone oil dispersion (Sofner AQ: Matsui Color Chemical Co., Ltd.) and 95 parts water at a drawing ratio of 70%. Drying, heat treatment at 130 ° C. for 3 minutes, and softening were performed.
As a result, a colored fabric with a softer texture than that of the colored fabric obtained in Example 4 was obtained.

(Comparative Example 1)
<Preparation of pigment dispersion>
A bead mill is prepared by mixing 25 parts of a phthalocyanine blue pigment (CI Pigment Blue 15: 3), 15 parts of a nonionic surfactant (Emulgen 911: manufactured by Kao Corporation), 5 parts of propylene glycol, and 55 parts of water. Dispersion was carried out for 2 hours using a glass bead having a diameter of 0.5 mm and a wet disperser to obtain a blue pigment dispersion 5 having a diameter of 0.263 μm.
The same procedure as in Blue Pigment Dispersion 5 was carried out except that the phthalocyanine blue pigment of Blue Pigment Dispersion 5 was replaced with an azo red pigment (CI Pigment Red 150). A red pigment having an average particle size of 0.249 μm Dispersion 6 was obtained.
<Adjustment of colored ink>
3 parts of blue pigment dispersion 5, 96 parts of turpentine reducer 1 and 1 part of antifoaming agent (SN deformer 777: manufactured by San Nopco Co., Ltd.) are blended and colored for screen printing with a viscosity of 13,800 mPa · s. Ink 9 was obtained.
Except that the blue pigment dispersion 5 of the color ink 9 was replaced with the red pigment dispersion 6, the same procedure was carried out as in the color ink 9 to obtain a color ink 10 for high mesh screen printing having a viscosity of 14,300 mPa · s.
<Coloring method>
Using the screen pattern of the above-mentioned colored ink 9 with a mesh pattern of 80 mesh / inch with a line width of 0.5 mm (horizontal) and the colored ink 10 with an 80 mesh / inch line width of 10 mm (vertical), an autoscreen on a cotton broad. 1000m continuous printing was performed using a printing machine, and after drying at 120 ° C with a dryer, heat treatment was performed at 140 ° C for 3 minutes to obtain a blue (horizontal) and red (longitudinal) checkered colored fabric. .
The obtained colored cloth had no change in the lattice width after the start of printing and after 1000 m processing, and the 0.5 mm line did not break due to clogging. Irregularity was conspicuous on a 10 mm wide grid, and the leveling property was inferior. Also, bleeding was seen in the picture, which was a problem with sharpness. In addition, the fastness of the obtained quality is that the wash fastness (JIS L-0217 103 method 5 times) is 1-2 grade, the friction fastness (JIS L-0849) is dry friction grade 1 and wet friction grade 1 It was extremely bad.

(Comparative Example 2)
<Tarpen reducer adjustment>
40 parts of water, 3 parts of nonionic surfactant (Emacol R-600: manufactured by Matsui Color Chemical Co., Ltd.), 2 parts of nonionic surfactant (Emulgen 105: manufactured by Kao Corporation), 55 parts of turpentine The terpene reducer 4 was obtained by uniformly mixing and emulsifying.
<Adjustment of colored ink>
3 parts of blue pigment dispersion 5, 66 parts of the above terpene reducer 4, 1 part of antifoaming agent (SN deformer 777: manufactured by San Nopco), emulsion type aqueous fixing agent (solid content 40 parts: Matsuminsol MR- 50: Made by Matsui Dye Chemical Co., Ltd.) 30 parts was blended to obtain a colored ink 11 for screen printing having a viscosity of 14,900 mPa · s.
Except that the blue pigment dispersion 5 of the color ink 11 was replaced with the red pigment dispersion 6, the same procedure was carried out as in the color ink 11 to obtain a color ink 12 for screen printing having a viscosity of 15,100 mPa · s.
<Coloring method>
Using a screen pattern with a grid pattern of 100 mm / inch line width of 0.5 mm (horizontal) and color ink 12 of 100 mesh / inch and a line width of 10 mm (vertical), the colored ink 11 is autoscreen printed on cotton broad. 1000 m continuous printing was performed using a machine, and after drying at 120 ° C. using a dryer, heat treatment was performed at 140 ° C. for 3 minutes to obtain blue (horizontal) and red (vertical) latticed colored fabrics.
The resulting colored cloth has a clogged lattice pattern after 1000 m processing, and the pattern is notched, and the 0.5 mm width pattern becomes a cut pattern. Irregularity occurred in a 10 mm wide grid, and the leveling property was poor. Also, bleeding was seen in the picture, which was a problem with sharpness. Further, the obtained colored fabric had a hard texture, poor water absorbability and a problem with air permeability, and was inferior to a colored product with a dye. Further, the fastness to washing (JIS L-0217 103 method 5 times) was 3-4 grade, the fastness to friction (JIS L-0849) was dry friction grade 3 and wet friction grade 2-3.

(Comparative Example 3)
<Coloring method>
Using the colored ink 11 used in Comparative Example 2, a line width of 0.5 mm (horizontal) with an 80 mesh / inch rotary screen plate and a line width of 10 mm with an 80 mesh / inch rotary screen plate using the colored ink 12 (Longitudinal) lattice pattern is printed on a polyester ponge using a rotary screen printing machine for 1000 m, dried at 120 ° C. with a dryer, and then subjected to heat treatment at 140 ° C. for 3 minutes. A colored cloth with a red (vertical) lattice pattern was obtained.
The obtained colored cloth after 1000 m processing was inferior in printability because mold scumming occurred during continuous printing, causing irritation on the printing surface, particularly a 10 mm wide grid.
Also, bleeding was seen in the picture, which was a problem with sharpness.
Furthermore, clogging occurred, and the 10 mm and 0.5 mm width symbols of the design became thinner and partially cut off. Further, the obtained colored fabric was hard as in Comparative Example 2, and was considerably inferior to the colored product by the dye. Further, the fastness to washing (JIS L-0217 103 method 5 times) was grade 3-4, the fastness to friction (JIS L-0849) was grade 3 dry friction, and grade 2-3 wet friction.

(Reference Example 1)
<Adjustment of colored ink>
5 parts of blue reactive dye (CI Reactive Blue 19), 5 parts of carboxymethyl cellulose (Fine Gum LV-2: Daiichi Kogyo Seiyaku Co., Ltd.), 5 parts of ethylene glycol, 3 parts of sodium bicarbonate, 82 of water The colored ink 13 was prepared by mixing the parts.
A colored ink 14 was obtained in the same manner as the colored ink 13 except that the blue reactive dye of the colored ink 13 was replaced with a red reactive dye (CI reactive red 121).
<Coloring method>
Using a screen pattern with a grid pattern of 120 mm / inch line width of 0.5 mm (horizontal) and colored ink 14 of 120 mesh / inch and a line width of 10 mm (vertical), the colored ink 13 is autoscreened on cotton broad. Using a printing machine, continuous printing of 1000 m was performed, and after drying, steam treatment was performed at 100 ° C. for 15 minutes, and then washing with water, soaping, and drying were performed in this order to obtain a colored printed fabric with a dye. The obtained colored product was soft and soft in texture, but some bleeding was observed and the line width was increased. In addition, the process is complicated and the production efficiency is inferior to that of the one printed with pigment, and there are problems of thermal efficiency and waste liquid.
The evaluation of the above Examples, Comparative Examples, and Reference Examples is shown in Table 1 below.

The following can be understood from the results of the above Examples, Comparative Examples, and Reference Examples.
(1) A colored cloth obtained when printing is carried out using a screen plate of 80 mesh / inch, using a pigment dispersed with a nonionic surfactant as a dispersant, and a colored ink comprising a terpenless reducer. There was no change in the grid width after the start of printing and 1000 m processing, and the 0.5 mm line was not clogged and clogged. However, mold scumming occurred during continuous printing, and on the printing surface, especially on the 10 mm wide grid. Irregularity is conspicuously inferior in levelness, bleed is seen at the time of painting, and sharpness is a problem, and fastness (fastness to washing, fastness to friction) is also deteriorated (Comparative Example 1).
(2) It was obtained when printing was performed using a screen plate of 100 mesh / inch using a colored ink composed of a pigment, a terpene reducer and a fixing agent dispersed with a nonionic surfactant as a dispersant. The colored fabric is clogged with a grid pattern after processing 1000 m, and the pattern becomes jagged, and the 0.5 mm width pattern becomes a cut pattern, and a pattern is formed during continuous printing, resulting in a printing surface, particularly 10 mm width. Irregularity occurs in the lattice, so that the leveling property and sharpness in painting are inferior, the texture becomes hard, and the water absorption and air permeability are also deteriorated (Comparative Example 2).
(3) In Comparative Example 3, when the 80 mesh / inch rotary screen plate was used instead of the 100 mesh / inch screen plate of Comparative Example 2, the obtained colored fabric was the same as in Comparative Example 2. It was of the quality of the grade (Comparative Example 3).
(4) When printing was performed using a 120-mesh / inch screen plate using a colored ink composed of a reactive dye, the resulting colored fabric was soft and soft, but slightly bled. The line width was increased, the process was complicated, and the production efficiency was inferior to that of the one printed with pigment, and problems of thermal efficiency and waste liquid also occurred (Reference Example 1).
(5) Colored ink obtained by diluting a coloring composition comprising a polymeric dispersant and a crosslinking agent comprising the hydrophobic group-containing monomer and the ionic group-containing monomer of the present invention as constituents with a terpenless reducer When the cross-linked printing was performed using a high-mesh screen plate, clogging or the like did not occur even though the printing was performed using a high-mesh screen plate. The quality (level dyeability, sharpness at the time of painting, fastness to washing, fastness to friction) is also good (Examples 1 to 6).
From the above, in this case, in view of the result of the comparative example, clogging occurs even when a colored ink using a large amount of a fixing agent is used, or when a low mesh screen plate of 100 mesh / inch or less is used. Etc. are expected to occur.
However, in the present invention, although a high mesh screen plate (150 to 350 mesh) in which clogging or the like is expected to occur as a screen plate is employed, clogging or the like does not occur and the screen plate is obtained. The colored fabric has an unprecedented superior effect that the texture is flexible and other qualities (level dyeability, sharpness in painting, fastness to washing, fastness to friction) are also good. In view of this, it can be seen that the selection of the cross-linking printing method using the high-mesh screen plate (150 to 350 mesh) using the color ink composed of the specific polymer dispersant and the cross-linking agent of the present invention has special significance. .

  The colored fiber product manufacturing method of the present invention makes it possible to manufacture a colored fiber product of excellent quality.

Claims (12)

  In the method for producing a colored fiber using a pigment, the average particle diameter is in the range of 0.1 to 0.5 μm by a polymer type dispersant having a hydrophobic group-containing monomer and an ionic group-containing monomer as constituent components. A coloring composition comprising a wet dispersion of a pigment dispersion and a crosslinking agent is diluted with a terpenless reducer to obtain a colored ink, and then the colored ink is applied to a fiber at a high mesh screen of 150 to 350 mesh / inch. A method for producing a colored fiber, wherein the pigment is fixed on the fiber by causing a crosslinking reaction between the ionic group of the polymer dispersant and the crosslinking agent by printing with a heat treatment and applying a heat treatment.   The method for producing a colored fiber according to claim 1, wherein the ionic group of the polymeric dispersant is a carboxyl group, a sulfonic acid group or a phosphoric acid group.   The method for producing colored fibers according to claim 1 or 2, wherein the polymer dispersant has a weight average molecular weight in the range of 2,000 to 50,000 and an acid value in the range of 100 to 250.   A compound having an oxazoline group, an isocyanate group, an ethyleneimine group, an aziridine group, a carbodiimide group, or a silane coupling group, or a blocked isocyanate group that reacts after heating, where the crosslinking agent reacts at room temperature or low temperature, The method for producing a colored fiber according to any one of claims 1 to 3, which is a compound having a hydrazide group or a diacetone acrylamide group.   The coloring according to any one of claims 1 to 4, wherein the wet dispersion uses a surfactant composed of polyoxyethylene aryl ether sulfate ester salt or polyoxyethylene alkyl ether sulfate ester salt as a dispersion aid. A method for producing fibers.   The method for producing a colored fiber according to any one of claims 1 to 5, wherein the terpene-less reducer contains a cross-linked acrylic resin as a thickener.   The method for producing a colored fiber according to any one of claims 1 to 6, wherein the cross-linking reaction is performed using a core-shell type aqueous resin as a fixing aid.   The fixing assistant is a water-soluble acrylic ester resin, a copolymer resin containing urethane ester, or a urethane resin, and the core component is a core-shell type aqueous resin made of a resin obtained by polymerizing a hydrophobic vinyl monomer. Item 8. A method for producing a colored fiber according to Item 7.   By using a terpeneless reducer in which the cross-linking reaction is blended in the range of 0.1 to 10 parts, preferably 0.1 to 6 parts, of a core-shell type aqueous resin with respect to 1 part of the pigment as a fixing aid, The method for producing a colored fiber according to claim 7 or 8, wherein a cross-linking reaction is caused between the polymer-type dispersant, the core-shell type aqueous resin and the cross-linking agent.   The method for producing colored fibers according to any one of claims 1 to 9, wherein the softening agent comprising silicone oil is blended in the colored ink or used as a post-treatment of the colored fibers.   A colored fiber manufacturing method, wherein the colored fiber obtained by the colored fiber manufacturing method according to claim 1 is further padded with silicone oil.   The colored fiber obtained by the manufacturing method of the colored fiber in any one of Claims 1-11 is a natural fiber, a semi-synthetic fiber, a synthetic fiber, or these mixed fibers.