Title of Invention	COLORING COMPOSITION AND COLORING METHOD
Abstract	The present invention provides a coloiing composition which comprises pigment particles whose average particle size is not more than 200nm and binder polymer particles. The composition permits the formation of a thin and uniform colored and coated layer on the surface of a fibrous structure mthout forming any color spot and without impairing the aesthetic properties and the flexibihty of the fibrous structure and it has a good color-developing ability and excellent fastness of color. The method for coloring a fibrous structure using this composition permits the coloration of even a mixed material using a single coloring composition and at a single coloration step and the method is quite simple, it can ensure a high working efficiency, a high energy efficiency and quite effective use of water resources and it is free of any environmental pollution.

Title of Invention

COLORING COMPOSITION AND COLORING METHOD

Abstract

The present invention provides a coloiing composition which comprises pigment particles whose average particle size is not more than 200nm and binder polymer particles. The composition permits the formation of a thin and uniform colored and coated layer on the surface of a fibrous structure mthout forming any color spot and without impairing the aesthetic properties and the flexibihty of the fibrous structure and it has a good color-developing ability and excellent fastness of color. The method for coloring a fibrous structure using this composition permits the coloration of even a mixed material using a single coloring composition and at a single coloration step and the method is quite simple, it can ensure a high working efficiency, a high energy efficiency and quite effective use of water resources and it is free of any environmental pollution.

Full Text	SPECIFICATION Coloring Composition and Coloring Method Technical Field The present invention relates to a coloring composition, a coloring method and an article colored with the coloring composition and more partictdarly to a coloring composition which permits the clear and uniform coloration of a substance to be colored such as a fibrous structure, a method for coloring such substance and an article colored with the coloring composition. Background Art As techniques for coloring articles (a substance to be colored), for instance, fibrous structures such as yams or threads, cloths, woven goods, knitted goods, and nonwoven fabrics, there have conventionally been tried a variety of coloring methods such as the dip dyeing technique in which a fibrous stmicture is dipped in a coloring composition, and the printing technique in which a fibrous structure is colored using a transfer-controlling plate such as a silk screen printing plate, a stencil printing plate, a rehef printing plate, an intaglio printing plate, and a lithographic printing plate. In the dip dyeing technique, a dye is used as a coloring dye, a fibrous structure is dipped in such a dye composition under heating and pressurizing conditions to thus make the dye penetrate into the fibrous structure, or such a fibrous structure is stirred and kneaded in the dye composition to uniformly adhere the dye to the structure and to thus prevent the formation of any color spot and/or the occurrence of any insufficient coloration. After the completion of the coloring step, the colored fibrous structure is washed with water or an aqueous solvent to remove any excess coloring component and to thus give a colored fibrous structure having good fastness of color without impairing the aesthetic property of the structure. There have been proposed various kinds of coloring dye compositions suitably used for coloring naturally occurring fibrous materials such as those obtained from cotton, hemp, silk, and wool fibers as well as synthetic fibrous materials such as those made of polyester, acrylic, rayon and nylon fibers, while appropriately selecting the kinds of dyes used as dyestviffs for coloration and they have widely been used for the coloration of a variety of fibrous materials such as those hsted above. However, this technique suffers from such a drawback that a specific dye should be properly selected depending on each particvdar fibrous material for the coloration since the technique makes use of a dye as a dyestuff for coloration. In particular, when coloring a mixed fibrous material comprising at least two different fibrous materials, this technique should use a plurality of coloring compositions or a plurahty of coloring steps. Moreover, the technique requires, in the coloring and/or washing processes, the use of a large quantity of energy and a large amount of industrial water for the heating, pressurizing, stirring and washing steps. This in turn leads to the discharge of a large amount of waste water and therefore, there has been desired for the development of a novel coloring method and a novel coloring composition in the fight of, for instance, the achievement of a high energy efficiency, the effective use of water resources and the prevention of any environmental pollution. In the printing (or dye transfer) technique, the transfer-controlling plate can be used for controUing the amount of the dye to be adhered and the area to which the dye is adhered when adheiing a coloring composition to a fibrous structure and accordingly, this technique is an excellent coloring method which permits the high quahty and highly precise coloration of, for instance, fine designs and patterns, pictorial symbols, dabbed patterns and/or gradated patterns. The coloring composition used in the dye trainsfer technique must be prepared so as to have such a viscosity that the transfer-controUing plate can normally show its function and in case of, for instance, a silk screen printing plate, the viscosity of the composition should be controlled to such a level that the composition does not cause any leakage through the mesh of the screen. The coloring agent used in this technique may be either dyes or pigments. When using a dye, the colored fibrous structure is washed with water or an aqueous solvent, after the coloring step, to remove any excess coloring component and to thus give a colored fibrous structure having good fastness of color without impairing the aesthetic property of the structure, like the dip dyeing technique. There have been proposed various kinds of coloring dye compositions suitably used for coloring naturally occurring fibrous materials such as those obtained from cotton, hemp, silk, and wool fibers as well as synthetic fibrous materials such as those made of polyester, acryUc, rayon and nylon fibers, while appropriately selecting the kinds of dyes to be used and they have widely been used for the coloration of a variety of fibrous materials such as those hsted above. On the other hand, when using a pigment, a binder shoiold be used for firmly adhering the pigment per se to a fibrous structure and accordingly, there has been used a coloring composition simultaneously comprising a polymer compound as a binder. However, the dye transfer technique, which makes use of a coloring composition containing a dye, likewise suffers from such a drawback that a specific dye should be properly selected depending on each particular fibrous material for the coloration since the technique makes use of a dye as a dyestuff for coloration. Like the dip dyeing technique. In particular, when coloring a mixed fibrous material comprising at least two different fibrous materials, this technique should use a plurahty of coloring compositions or a plurality of coloring steps. Accordingly, this technique requires, in the coloring and/or washing processes, the use of a large quantity of energy and a large amount of industrial water for the heating, pressurizing, stirring and washing steps. This in turn leads to the discharge of a large amount of waste water. Therefore, there has likewise been desired for the development of a novel coloring method and a novel coloring composition in the light of, for instance, the achievement of a high energy efficiency, the effective use of water resources and the prevention of any environmental pollution. Moreover, the dye transfer technique, which makes use of a coloring composition containing a pigment, also suffers from drawbacks such that particles of the pigment and/or the polymer compound used as a binder are adhered to the surface of a transfer-controlling plate and this in turn results in the reduction of the amount of the composition adhered to the fibrous structure and the area thereof to be colored and that the pigment and/or the polymer compound adhered to the fibrous structure may reduce the aesthetic properties and flexibUity of the fibrous structure. For this reason, there has been desired for the development of a novel coloring composition. Patent Document 1 discloses a coloring agent for use in the dip dyeing technique, whose particle size is not more than 0.5 /i m, a colored article obtained using the composition and a coloring method which makes use of the same. However, the coloring dyestuff used in this coloring agent is a disperse dye and accordingly, this method does not improve or eliminate the problems of the appropriate selection of the material for a fibrous structure due to the use of a dye; the requirement for the use of complicated steps; the requirement for large quantities of energy and industrial water; the delivery of a large quantity of waste water. In addition, Patent Document 2 discloses an ink composition whose particulate materials as the components thereof have a particle size of not more than 10 jixa and a screen printing method which makes use of the ink, but this technique has not yet satisfactorily solved the problems concerning the impairment of the aesthetic properties and the flexibihty of the fibrous structure to be treated. Patent Document 1- Japanese Un-Examined Patent PubHcation 2003-313454; Patent Document 2* Japanese Un-Examined Patent Publication 2004-195697. Disclosure of the Invention Problems That the Invention is to Solve Accordingly, it is an object of the present invention to provide a coloring composition which can eliminate the drawbacks associated with the foregoing conventional techniques and a coloring method which makes use of the composition. It is another object of the present invention to provide a coloring composition which has a good color-developing ability and excellent fastness of color and which would permit the formation of a thin and uniform colored and coated layer on the surface of a fibrous structure without impairing the aesthetic properties of the fibrous structure. It is still another object of the present invention to provide a coloring composition which has a high color-developing abihty is not accompanied by the formation of any color spot and which permits the coloration of any fibrous structure irrespective of the kinds of their materials, without causing the reduction of the aesthetic properties and flexibility of the fibrous structure. It is a further object of the present invention to provide a method for coloring even a naiixed material using a single coloring composition and at a single step. It is a still further object of the present invention to provide a method for coloring a fibrous structural material, which is qxxite simple, can ensure a high working efficiency, a high energy efficiency and quite effective use of water resources and which is free of any environmental pollution. It is a stiU further object of the present invention to provide a coloring method which does not require the use of any washing step, requires the use of a reduced quantity of energy, provides only a small amount of waste water, ensures effective use of water resources and is free of any environmental pollution. It is a still further object of the present invention to provide an article colored by the foregoing coloring composition. Means for the Solution of the Problems The inventors of this invention have conducted various studies, have found that the foregoing objects of the present invention can be accomplished by the use of a pigment having a specific particle size as the dyestuff for the coloration and by adjusting the average particle size of the whole particles dispersed in a coloring composition including the pigment particles to a level of not more than 200 nm and have thus completed the present invention. According to the present invention, there are thus provided the following coloring composition and the following coloring method which makes use of the coloring composition: 1. A coloring composition comprising pigment particles whose average particle size is not more than 200nm and binder polymer particles. 2. The coloring composition as set forth in the foregoing item 1, wherein the composition comprises binder polymer particles having an average particle size of not more than 200nm. 3. The coloring composition as set forth in the foregoing item 1 or 2, wherein the pigment particles are ones subjected to a hydrophihzation treatment. 4. The coloring composition as set forth in any one of the foregoing items 1 to 3, wherein the pigment particles are hydrophilized with a dispersant consisting of a surfactant and a water-soluble polymer. 5. The coloring composition as set forth in the foregoing item 4, wherein the pigment particles are ones each comprising at least one hydrophilic group selected from the group consisting of hydroxyl group, carboxyl group and amino group. 6. The coloring composition as set forth in any one of the foregoing items 2 to 5, wherein the binder polymer particles have a Tg value (glass transition point) of not higher than 10°C and an average particle size ranging from lOnm to lOOnm. 7. The coloring composition as set forth in any one of the foregoing items 1 to 6, wherein the average particle size of the pigment particles falls within the range of from lOnm to lOOnm. 8. The coloring composition as set forth in any one of the foregoing items 1 to 7, wherein the composition has a viscosity ranging from 1000 to 200,000mPa- s. 9. The coloring composition as set forth in any one of the foregoing items 1 to 7, wherein the composition has a viscosity ranging from 10 to l,000mPa-s. 10. A method for the dye transfer-coloration of a fibrous structure characterized in that it uses the coloring composition as set forth in the foregoing item 8. 11. The method for the dye transfer-coloration as set forth in the foregoing item 10, wherein the fibrous structure is dye transfer-colored according to the silk screen printing technique, while using a high mesh screen having a mesh size of not less than 120 mesh and a rubber squeegee having a Shore hardness ranging from 40 to 90 degrees. 12. A method for the dip-coloration of a fibrous structure comprising using the coloring composition as set forth in the foregoing item 9. 13. The method for the dip-coloration as set forth in the foregoing item 12, wherein the rate of pickup falls within the range of from 50 to 90%. 14. An article colored with a coloring composition as set forth in any one of the foregoing items 1 to 9. 15. The article as set forth in the foregoing item 14, wherein it is a fibrous structure. Effects of the Invention The coloring composition and coloring method of the present invention make use of pigment particles, as a dyestuff for coloration, whose average particle size is not more than 200nm and polymer particles, as a binder, preferably having an average particle size of not more than 200nm and therefore, they can form a thin and uniform colored and coated layer on the surface of a fibrous structure \^dthout impairing the aesthetic properties of the fibrous structure; they can ensure a good color-developing ability and excellent fastness of color; they permit ) the coloration of even a mixed material using a single coloring composition and by a single coloring step; they can further ensure a high working efficiency, a high energy efficiency and quite effective use of water resources and they are substantially free of any environmental pollution. It is considered that the following are the reasons why the coloring composition and coloring method of the present invention are excellent as compared with the conventional ones- The conventional fiber-coloring composition which makes use of a pigment undergoes adhesion to the fibrous structure, forms a thick color-developing coated layer since the particles of the pigment and a binder poljoner used therein have a large particle size. Accordingly, it has not provided any clear color-development and, in turn, any colored fibrous structure having good aesthetic properties. On the other hand, the coloring composition and coloring method of the present invention make use of a pigment and a polymer binder, which have been finely pulverized to a specific particle size. Accordingly, they can form a thinner colored, coated layer, while the aesthetic properties of the resulting colored fibrous structure can be maintained or even improved, the generation of voids in the coated layer can be hmited to a lowest possible level, the resulting article has an improved fastness of color and they also ensure a clear color-development. Best Mode for Carrying Out the Invention Various modes for carrying out the present invention will hereunder be described in more detail. In the present invention, the term "fibrous structure" means yarns or threads, cloths, woven goods, knitted goods, nonwoven fabrics, paper, plates, leather and other sheet-like products, as well as articles prepared from these products, which are made of natural fibers, synthetic fibers, semi-synthetic fibers or mixture thereof. The coloring composition of the present invention is characterized in that it uses a pigment whose average particle size is not more than 200nm as a dyestuff component for coloration and the composition is preferably characterized in that it comprises polymer particles having an average particle size of not more than 200nm as a binder component. As the dyestuff component for coloration used in the coloring composition of the present invention, usable herein include aU of the inorganic and organic pigments which can be dispersed in water and an aqueous solvent and have chromatic colors. Moreover, it is also possible to use pseudo-pigments obtained by pigmenting resin emulsions with dyes or the like. Such inorganic pigments may be, for instance, metal powder and powdery metal-containing compounds, while such organic pigments may be, for instance, azo lake pigments, insoluble azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dye lake pigments, nitro pigments, and nitroso pigments. More specifically, examples of pigments usable herein include inorganic pigments, for instance, carbon black such as channel black, furnace black and thermal black, titanium black, iron black, lead black, copper-chromium black, cobalt black, red iron oxide, chromium oxide, cobalt blue, yellow iron oxide, viridian, cadmium yellow, vermihon, cadmium red, lead yellow, molybdate orange, zinc chromate, strontium chromate, ultramarine blue, barite powder, iron blue, manganese violet, aluminum powder, and brass powder; and organic pigments such as aniline black, perylene black, cyanine black, pseudo-pigments obtained by pigmenting resin emulsions with black dyes, C.I. Pigment Blue 1, C.I. Pigment Blue 15, C.I. Pigment Blue 17, C.I. Pigment Blue 27, C.I. Pigment Red 5, C.I. Pigment Red 22, C.I. Pigment Red 38, C.I. Pigment Red 48, C.I. Pigment Red 49, CI. Pigment Red 53, C.I. Pigment Red 57, CI. Pigment Red 81, CI. Pigment Red 104, CI. Pigment Red 146, CI. Pigment Red 245, CI. Pigment Yellow 1, CI. Pigment Yellow 3, CI. Pigment Yellow 4, CI. Pigment Yellow 12, CI. Pigment Yellow 13, CI. Pigment Yellow 14, CI. Pigment Yellow 17, CI. Pigment Yellow 34, CI. Pigment Yellow 55, C.I. Pigment Yellow 74, C.I. Pigment YeUow 83, C.I. Pigment YeUow 95, C.I. Pigment Yellow 166, CI. Pigment Yellow 167, CI. Pigment Orange 5, CI. Pigment Orange 13, CI. Pigment Orange 16, CI. Pigment Violet 1, CL Pigment Violet 3, CI. Pigment Violet 19, CI. Pigment Violet 23, CI. Pigment Violet 50, and CL Pigment Green 7, In the present invention, the foregoing pigments may be used alone or in any combination of at least two of them. The average particle size of the pigment particles present in the coloring composition of the present invention is not more than 200nm and preferably not more than lOOnm. This is because if the coloring composition contains pigment particles whose average particle size exceeds 200nm, the surface roughness of the resulting colored fibrous structure increases and this accordingly leads to the increase of the frictional resistance and the corresponding reduction of the fastness to rubbing. On the other hand, if the coloring composition contains pigment particles whose average particle size is less than lOnm, the resulting coloring composition is Hable to cause the reduction of, for instance, the color density developed and the weatherabihty. Therefore, the average particle size of the pigment particles used in the present invention preferably ranges from 10 to 200nm and more preferably 20 to lOOnm. As the means for controUing the average particle size of the pigment particles, usable herein includes, for instance, a method comprising the steps of adding, to the foregoing pigment, water and an aqueous solvent and optionally a wetting agent, a moisturizing agent, a dispersion stabilizer or the Like and then blending them using a shear force-applying tj^e dispersion device currently used in this field. For instance, the foregoing mixture is processed using, for instance, a stirring type dissolver, a homomixer, a Henschel mixer, a medium-type ball mill, a sand mill, an attritor, a paint-shaker, a medium-less type three-roll or five-roU mill, a jet mill, a water-jet mill or an ultrasonic dispersion device for a predetermined period of time to thus give pigment particles having an intended average particle size. In addition, desired pigment particles having a predetermined average particle size can more certainly be prepared when by pulverizing and dispersing the pigment in a dispersion device and then optionally removing coarse particles and extremely fine particles present in the resvdting pigment particles. The pigment particles other than those having a desired particle size may be removed by, for instance, the static settling technique, the centrifiigal sedimentation technique, or the removal through filtration. The pigment particles used in the present invention are quite fine and accordingly, they may again undergo agglomeration due to any external factor or upon the coloring process to thus impair the desire quality of the coloring composition. To prevent such re-agglomeration of the pigment particles, it is preferred to subject the surface of the pigment particles to a hydrophihzation treatment in advance. Examples of such hydrophilization treatments are those comprising the step of imparting, to the surface of pigment particles, hydrophihc groups such as hydroxyl, carboxyl, and/or amino group through the treatment of the pigment particles with a dispersing agent containing a surfactant and/or a water-soluble polymer to thus improve the stability of the particles. Examples of such surfactants usable herein are anionic ones such as alkyl carboxyhc acid esters, alkyl-sulfuric acid esters and alkyl-phosphoric acid esters; cationic ones such as aliphatic ammonium salts; and nonionic ones such as alkyl ethers, fatty acid ester ethers and sorbitan fatty acid esters. In addition, examples of the foregoing water-soluble polymers usable herein include polymeric dispersing agents such as poljrvinyl pyrrohdone, polyvinyl alcohols, acrylics (such as low molecular weight polyacrylic acids and polyCmethacryhc acids)), poly(maleic adds), copolymers of styrene with acryhc acid, methacryhc acid or the hke, poly amides and rosin-modified maleic acids. Furthermore, it is also possible to hydrophilize the surface of pigment particles using a treatment with an alkali such as sodium hydroxide, a treatment with an oxidizing agent such as chromic acid, or a topochemical treatment such as the low temperature plasma treatment. Among the hydrophihc groups which can he imparted to the surface of the pigment particles, hydroxyl and carboxyl groups are particularly preferred since they may cause a cross-hnking reaction with hinder polymer molecules and a crosslinking agent during the coloration of a fibrous structure and this may in Uxm result in the effect of improving the fastness of the color. The content of the pigment particles in the coloring composition of the present invention preferably ranges from 0.1 to 15% by mass and more preferably 0.5 to 10% by mass based on the total mass of the coloring composition. This is because if the content thereof is less than 0.1% by mass, there is observed such a tendency that the resulting composition does not show any satisfactory color development, while if it exceeds 15% by mass, the resulting coloring composition has such a tendency that the fastness thereof to rubbing is reduced. The binder polymer used in the present invention should be one capable of being dispersed in water and an aqueous solvent in the form of fine particles preferably having an average particle size of not more than 200nm and more preferably not more than lOOnm. On the other hand, if the coloring composition contains a binder polymer whose average particle size exceeds 200nm, there may be observed the following tendency- the thickness of the coated layer formed by the binder polymer increases and this in turn leads to the deterioration of the aesthetic properties of the fibrous structure colored by the composition and the ability of the binder polymer to bind the pigment particles is reduced and this accordingly results in the reduction of the fastness thereof to rubbing. On the other hand, if binder polymer particles having an average particle size of less than lOnm are present in the coloring composition, there may be such a tendency that the liquid coloring composition becomes unstable due to the agglomeration of such fine particles. For this reason, the average particle size of the binder particles used in the present invention preferably ranges from 10 to 200nm and more preferably 20 to lOOnm. In particular, it is quite preferred to use the binder polymer particles, whose average particle size is controlled in such a manner that it falls within the range of from 10 to lOOnm, since the use thereof permits the formation of a micro-coat as a coated layer formed from the binder polymer, while maintaining the aesthetic properties of the fibrous structure and the use likewise permits the improvement of the abihty of the binder polymer to bind the pigment particles. The binder polymer used in the present invention desirably has a glass transition temperature of preferably not higher than 10°C and more preferably not higher than 5°C. If the glass transition temperature of the binder polymer exceeds 10°C, the binder polymer insufficiently forms a coated film when the coloring method of the present invention is appHed to a fibrous structure in such a working environment maintained at room temperature (20'C± 10°C) and a large number of voids are formed in the resulting film. There is observed such a tendency that these voids remains in the film even after the heat-treatment thereof and this accordingly reduces the strength of the coated layer made of the binder polymer. On the other hand, if the glass transition temperature of the binder polymer is less than 10°C, the binder polymer can form a uniform film even at room temperature to thus prevent any reduction of the strength of the resulting film. The binder polymer used in the present invention is not restricted to any specific one inasmuch as it may satisfy the foregoing reqviirements and examples thereof include easily available and commonly used ones such as acrylic polymers, acryhc monomer-styrene copolymer, acryhc monomer-urethame copolymers, acryHc monomer-maleic acid copolymers, acryhc monomer-butadiene copolymers, acryhc monomer-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, polyurethanes and poly olefins. The binder polymer used in the present invention may be in the form of, for instance, an emulsion or a dispersion. The content of the binder poljrmer particles in the coloring composition of the present invention preferably ranges from 0.5 to 20% by mass and more preferably 1 to 10% by mass based on the total mass of the coloring composition. This is because if the content thereof is less than 0.5% by mass, there is observed such a tendency that the binder polymer does not show its abihty as a binder and the resulting composition shows a reduced fastness to rubbing, whUe if it exceeds 20% by mass, the resulting coloring composition has such a tendency that the aesthetic properties of the fibrous structure processed with the composition are impaired. The coloring composition of the present invention can be used for the coloration of a variety of articles. Examples of such articles are fibrous structures such as yarns or threads, cloths, woven goods, knitted goods, nonwoven fabrics, paper, plates, and leather. The coloring methods particularly preferably used for coloring fibrous structures include, for instance, the dye transfer technique and the dip dyeing technique. When coloring a fibrous structure according to the dye transfer technique, the coloring composition used in the technique should have such a viscosity that the transfer-controUing plate can normally show its function. For instance, in case where a silk screen printing plate is used, the viscosity of the composition should be controlled to such a level that the composition does not cause any leakage through the mesh of the screen used. For instance, when using a silk screen printing plate having a large pore size on the order of 60 mesh, filaments each having a diameter of 83 M m are usually used, the screen has a rate of opening of 65% and a pore size of 340 jx m and accordingly, the composition should have a viscosity at which the coloring agent does not permeate into the screen even at a penetration volume of 55 cm^/m^. The coloring composition of the present invention comprises pigment particles and binder polymer particles, having a quite small particle size and therefore, the viscosity thereof should be controlled to a level of not less than 5,000mPa"S and preferably not less than 20,000mPa'S. However, if the viscosity thereof is too high on the order of higher than 200,000mPa'S, the meshes of the screen printing plate are plugged with the coloring composition and accordingly, the coloration of a fibrous structure is liable to be insufficient. For this reason, when using a silk screen printing plate having a large pore size on the order of 60 mesh, the coloring composition used should have a viscosity preferably ranging from 5,000 to 200,000mPa-s and more preferably 20,000 to 100,000mPa-s. On the other hand, when using a silk screen printing plate having a small pore size on the order of 120 mesh, filaments each having a diameter ranging from 48 to 83 M m are usually used, the screen has a rate of opening of 49% and a pore size of 152 /i m and accordingly, the composition used should have a viscosity at which the coloring composition does not permeate into the screen even at a penetration volume of 39 cm^/m^ and which also permits the appropriate passage of the composition through the screen mesh when appljdng a pressure with a squeegee. To prevent the permeation of any coloring composition through the screen, the viscosity of the composition is desirably controlled to a level of not less than 3,000mPa'S and preferably not less than 15,000mPa'S. However, if the viscosity thereof exceeds 150,000mPa-s, when pressurizing the screen with a squeegee, the meshes of the screen printing plate are plugged with the coloring composition and accordingly, the coloration of a fibrous structure is liable to be insufficient, because of the extremely high viscosity of the composition. Accordingly, when using a silk screen printing plate having a small pore size on the order of 120 mesh, the coloring composition used should have a viscosity preferably ranging from 3,000 to 150,000mPa-s and more preferably 15,000 to 80,000mPa-s. When using a silk screen printing plate having a pore size of 230 mesh for the purpose of accomplishing the high quahty and high precision dye transfer coloration, filaments each having a diameter ranging from 48 to 67 M m are usually used, the screen has a rate of opening of 28% and a pore size o£ 65 iixn and accordingly, the coloring composition used should have a viscosity at which the composition does not permeate into the screen even at a penetration volume of 22 cm^/m^ and which also permits the appropriate passage of the composition through the screen mesh when applying a pressure with a squeegee. To prevent the permeation of any coloring composition through the screen, the viscosity of the composition is desirably controlled to a level of not less than l,000mPa-s and preferably not less than 2,000mPa-s. However, if the viscosity thereof exceeds 120,OOOmPa'S, when pressurizing the screen with a squeegee, the meshes of the screen printing plate are plugged with the coloring composition and accordingly, the coloration of a fibrous structure is Hable to be insufficient, because of the extremely high viscosity of the composition. Accordingly, when using a silk screen printing plate having a finer pore size on the order of 230 mesh, the coloring composition used should have a viscosity preferably ranging from 1,000 to 120,000mPa-s and more preferably 2,000 to 70,000mPa'S. When coloring, in this way, fibrous structures using the coloring composition of the present invention according to the dye transfer technique, the viscosity of the coloring composition should be adjusted while taking into consideration the mesh size, pore size and penetration volume of the silk screen printing plate. Thus, high quality and high precision pictorial symbols, dabbed patterns and/or gradated patterns can be colored at high resolution. The squeegee used in the coloring method according to the present invention should be one which can apply a desired pressure to the coloring composition present on the silk screen printing plate, can satisfactorily make the composition pass through the openings of the screen printing plate and can appropriately scratch off the unnecessary coloring composition from the silk screen and accordingly, the squeegee should have appropriate elastic characteristics. If the squeegee has a Shore hardness of not more than 35 degrees, the resulting squeegee is insufficient in its strength and it may immediately be worn out, while if the Shore hardness thereof is higher than 91 degrees, the resulting squeegee has insufficient elastic characteristics and accordingly, the squeegee does not serve to appropriately scratch off, from the silk screen, the unnecessary coloring composition. For this reason, the hardness of the squeegee used in the coloring method of the present invention more preferably ranges from 40 to 80 degrees and the squeegee would have highly satisfied physical properties and excellent durabihty inasmuch as the hardness thereof falls within the range specified above. The usual elastic molded articles and resins commercially available can be used as the material for forming such a squeegee without any restriction insofar as they satisfy the foregoing requirement for the physical properties or the Shore hardness specified above. Specific examples thereof are acrylic rubber, acryhc urethane rubber, acryhc nitrile rubber, acrylic butadiene rubber (acryhc acid or methacryhc acid-butadiene rubber), urethane rubber, butadiene rubber, butyl rubber, NBR (acrylonitrile-butadiene rubber), epoxy elastomers and fluororubber. Various kinds of thickening agents can be used for controlling the viscosity of the coloring composition according to the present invention. Such a thickening agent may be, for instance, at least one member selected from the group consisting of synthetic polymers, cellulose materials and polysaccharides and terpene emulsions, which naay be used alone or in any combination of at least two of them. Specific examples of the foregoing synthetic poljnners are polyacryhc acids, polyvinyl alcohol, polyethylene oxide, polyAdnyl pyrrolidone, polyvinyl methyl ether, and polyacrylamide. Specific examples of cellulose materials are ethyl cellulose, methyl cellulose, hydroxymethyl cellulose, and carboxymethyl cellulose. Specific examples of the foregoing polysaccharides are xanthane gum, guar gum, casein, gum arabic, gelatin, carrageenan, alginic acid, tragacanth gum, locust bean gum, and pectin. Specific examples of the foregoing terpene emulsions include mousse-like emulsions each obtained by emulsifying a mixture of mineral terpene and water with a nonionic surfactant. In case where a fibrous structure is colored using the coloring composition of the present invention according to the dip dyeing technique, the viscosity of the coloring composition should be controlled so that the fibrous structure is wetted with the coloring composition to thus stably adhere the pigment and the binder poljnner to the fibrous structure. In particular, if the viscosity of the composition is too low and when the pigment as the dyesttxff for the coloration is in the fine particulate state, the pigment adhered to the fibrous structure may migrate from the course area to the dense portion of the structure due to the capillary phenomenon thereof when drjong the structure provided thereon with the coloring composition adhered thereto and this in turn leads to the formation of color spots and any uniformly colored product cannot be obtained at all. For this reason, the viscosity of the composition is preferably adjusted to a level of not less than lOmPa-s. However, when the viscosity of the coloring composition exceeds lOOOmPa-s, the composition would hardly penetrates into the fibrous structure. Therefore, when coloring the fibrous structure according to the dip dyeing technique, the coloring composition of the present invention preferably has a viscosity ranging from 10 to lOOOmPa-s, and more preferably 20 to 500mPa-s. The use of the coloring composition whose viscosity is adjusted to a level falling within the range specified above permits the formation of a satisfactorily colored fibrous structure according to the dip dyeing technique. When coloring a fibrous structure with the coloring composition of the present invention according to the dip dyeing technique, the aesthetic properties and color-developing ability of the structure may variously vary depending on the amount of the coloring composition adhered thereto. Accordingly, the rate of pickup of the coloring composition (the adhered amount (by mass) of the composition (prior to drjdng) based on the amount (lOO parts by mass) of the fibrous structure) preferably ranges from 50 to 91% and more preferably 60 to 80%. If the rate of pickup is less than 50%, the adhered amount of the composition is too low to give a colored product having a satisfactory hue corresponding to the sufficient coloration, while if it exceeds 91%, the adhered amoxmt of the composition is too high and this accordingly leads to the formation of a colored fibrous structure provided with an extremely thick coated layer and having impaired aesthetic properties. Thus, the use of the coloring composition of the present invention whose rate of pickup is adjusted to a level specified above permits the formation of a colored fibrous structure excellent in the color-developing ability, the aesthetic properties and the fastness of color. In the fibrous structures colored using the coloring composition of the present invention according to the dip dyeing technique and the dye transfer technique, the pigment as the coloring dyestxiff is held on the surface of the fibers preferably by the action of the polymer biader and accordingly, the method of the invention does not require the use of any additional step for removing, for instance, any excess coloring agent, any sizing agent and any additive through washing with water after the coloration with the coloring composition and the subsequent drying operation. Moreover, the coloring method of the present invention using the coloring composition of the present invention does not require the selection of any appropriate dye suitably used for each particular fibrous material and the control of heating, pressurizing and stirring conditions for properly making the dye penetrate into the fibrous structure. Accordingly, the coloring method of the present invention permits the coloration of even a mixed material using a single coloring composition and a single step for coloration and accordingly, it can be said that the coloring method of the present invention is an excellent coloring method since it is excellent in the working efficiency and the energy efficiency, and it permits the effective use of the water resources and it is free of any environmental pollution. The coloring composition of the present invention uses, as the solvent, water (for instance, tap water, distilled water, purified water, deionized water, pure water and deep sea water). In addition to water, however, it is also preferred to use an aqueous medium other than water having a polar group which makes the medium compatible with water, which can impart water retention characteristics to the resulting composition and improve the stabihty of the pigment and the binder polymer. Examples of such aqueous mediums are methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, ethylene glycol monomethyl ether, glycerin, and pyrrohdone. In addition to these aqueous mediums, usable herein also include, for instance, non-aqueous solvents such as hquid paraffin, mineral oils and industrial gasoline, insofar as they can be blended with water or dispersed therein through the use of, for instance, an emulsifying agent. These solvents may be used alone or in any combination. The content of water in the coloring composition of the present invention preferably ranges from 10 to 90% by mass and more preferably 30 to 80% by mass. When the binder polymer is used alone in the coloring composition of the present invention, the resulting film may sometimes be insufficient in the strength and fastness thereof. In this case, the fastness of the resulting film can be improved by the incorporation, into the coloring composition, of a crossHnking agent which can undergo a crosshnking reaction with, for instance, hydroxyl and/or carboxyl groups present in the pigment and the binder polymer. In this respect, the following crossHnking reactions can be used- the dehydration condensation reaction of methylol groups with hydroxyl groups; the epoxy ring-opening polymerization reaction of glycidyl groups with hydroxyl groups; the urethane-forming reaction of isocyanate groups with hydroxyl and/or carboxyl groups; the amide ester-forming reaction of oxazoHne groups with carboxyl group; the carbamoylamide-forming and isourea-forming reaction of carbodiimide groups with hydroxyl and carboxyl groups; the condensation dehydration reaction of silanol groups with hydroxyl groups; the dehydration condensation reaction of metal alkoxide groups with hydroxyl groups; the melamine-condensation reaction of polj^unctional methylol groups with hydroxyl groups; and the reduction dehydration reaction of diacetone acryiamide with hydrazide and hydroxyl groups. When incorporating these aqueous crosshnking agents into the coloring composition and then heating the restdting mixture, the hydroxyl and carboxyl groups of the pigment and/or the binder polymer undergo a crosshnking reaction with the crosshnking agents to form a three-dimensional network and as a result, the fastness of the resulting film may substantially be improved. The content of the crosshnking agent in the coloring composition of the present invention preferably ranges from 0.1 to 5% by mass and more preferably 0.2 to 2.5% by mass. The coloring composition of the present invention may further comprise, in addition to the foregoiug components, other optional additives commonly or widely used in the coloring composition in an amount which does not adversely affect the intended effects of the present invention, for instance, an antiseptic agent, an antifungal agent, a sequestering agent, a pH-adjusting agent, a lubricant, and/or a wetting agent. Examples of such antiseptic and antifungal agents include phenols, sodium omadine, sodium pentachlorophenol, l,2-benzisothiazohn-3-one, 2,3,5,6-tetrachloro-4-(methyl-sulfonyl) pyridine, sodium benzoate, alkah metal salts of benzoic acid, sorbitan fatty acid and dehydro-acetic acid, and benzimidazole type compounds. Examples of such sequestering agent are benzotriazole, dicyclohexyl ammonium nitrite, di-isopropyl ammonium nitrite, tolyl triazole, and saponins. Examples of the foregoing pH-adjusting agent include urea, aqueous ammonia, monoethanolamine, triethanolamine, aminomethyl propanol, alkah metal salts of phosphoric acid such as sodium tripolyphosphoate and alkah metal hydroxides such as sodium hydroxide. Examples of the foregoing lubricants and wetting agents are polyalkylene glycol derivatives such as polyoxyethylene lauryl ether, alkah metal salts of fatty acids, silicone oil emulsions, polyether-modified silicones such as polyethylene glycol adducts of dimethylene polysiloxane, poly(tetrafluoroethylene) powder, fluorochemical surfactants, fluorine-modified oils and acetylene glycol. Examples Then the present invention will be described in more detail with reference to the following Pigment-Preparation Examples, Examples and Comparative Examples, but the present invention is not restricted to these specific Examples at all. Pigment-Preparation Example 1" Pigment-Preparation Example Using Paint Shaker (Pigment l): There was dispensed each of the foregoing components in the amount specified above, the components thus dispensed were stirred in a dissolver to give a uniform dispersion and then the resulting formvdation was stirred in a paint shaker for 8 hours under such a condition that the bead-packing rate by volume was set at 60% to thus give Pigment 1. The average particle size of pigment particles included in the resulting product of this pigment-preparation example 1 was determined using NICOMP 380ZLS (available from NOZAKI Sangyo Co., Ltd.) and lOOnra polystyrene particles (3100A) and 300nm polystyrene particles (3300A), as reference materials, which were available from Duke Scientific Corporation and had been authorized by NIST (National Institute of Standards and Technology) according to the laser-diffraction technique and as a result, it was found to be 90nm. Pigment'Preparation Example 2- Pigment-Preparation Example Using Paint Shaker (Pigment 2): There was dispensed each of the foregoing components in the amount specified above, the components thus dispensed were stirred in a dissolver to give a uniform dispersion and then the resulting formvdation was stirred in a paint shaker for 10 hours at a bead-packing rate by volume set at 60% to thus give Pigment 2. The average particle size of pigment particles included in the resulting product of this pigment-preparation example 2 was determined according to the laser-diffraction technique and as a result, it was found to be 80nm. Comparative Pigment 1^ Pigment 3^ Ryudye-W Black RC cone (6) The average particle size of pigment particles included in this comparative pigment 1 was determined according to the laser-diffraction technique and as a result, it was found to be 2.2 M m. Comparative Pigment 2- Pigment 4- New Lacqutimine Standard Red FL3G cone (7) The average particle size of pigment particles included in this comparative pigment 2 was determined according to the laser-diffraction technique and as a result, it was found to be 760nm. Stock Sizing Formulation i: Thickening Agent 2 There was dispensed each of the foregoing components in the amount specified above, the components thus dispensed were treated for the emulsification thereof using a homomixer to give a mousse-hke thickening agent and the latter was used as the thickening agent for the preparation of the products of the following Examples and Comparative Examples. Examples 1 to 4 and Comparative Examples 1 to 3 Each coloring composition was prepared using the components hsted in the following Tables 1 and 2 according to the compositions likewise specified in these Tables and then fibrous structures were colored using these coloring compositions according to the coloring methods specified below. In this connection, there were evaluated the physical properties and the working properties during the coloring operations of the coloring compositions prepared in Examples and Comparative Examples and the aesthetic properties and the fastness to rubbing of the colored fibrous structures, according to the following evaluation methods= (Method for Determining Average Particle Size) Each of the coloring compositions prepared in the foregoing Examples and Comparative Examples was diluted 100 times with deionized water and the average particle size of the pigment particles dispersed therein was determined using NICOMP 380ZLS (available from NOZAKI Sangyo Co., Ltd.) and lOOnm polystyrene particles (3100A) and 300nm polystyrene particles (3300A), as reference materials, which were available from Duke Scientific Corporation and had been authorized by NIST (National Institute of Standards and Technology) according to the laser-diffraction technique. (Method for the Determination of Viscosity) The viscosity of the coloring compositions prepared in the foregoing Examples and Comparative Examples was determined at 25°C and at 0.5 rpm using TV-30 type Viscometer^ Cone Plate t5T)e Standard Rotor (available from TOKI Sangyo Co., Ltd.). (Mesh-Permeation Test l) (Dye transfer technique/Leakage characteristics) Each of the coloring compositions prepared in the foregoing Examples and Comparative Examples was allowed to stand, for 4 hours, on a silk screen printing plate having a fine mesh size of 120 (TG-1200 available from MURAKAMI Screen Co., Ltd.) to thus examine the leakage of the coloring composition through the screen with the naked eyes. O- There was not observed any leakage of the coloring composition; A: There was not observed any leakage of the coloring composition, but the liquid moiety thereof permeated through the screen; X: There was observed the leakage of the coloring composition. (Mesh-Permeation Test 2) (Dye transfer technique/Uniformity of coloration) Each of the coloring compositions prepared in the foregoing Examples and Comparative Examples was allowed to stand, for 10 minutes, on a silk screen printing plate having a fine mesh size of 120 (TG-1200 available from MURAKAMI Screen Co., Ltd.) and then a solid pattern was printed on the whole surface of a polyester taffeta (available fi:om IROZOME Co., Ltd.) with each composition using a squeegee made of urethane rubber having a Shore hardness of 50 degrees according to the dye transfer technique, dried at 120°C for one minute and the fibers thus colored were visually inspected for the uniformity of the coloration thereof. O- The whole surface was uniformly colored; A- There were observed the presence of some small voids; X: There was observed the presence of distinct un-colored area. (Color Spots Test) (Dip dyeing technique/Uniformity of coloration) A polyester taffeta (available from IROZOME Co., Ltd.) was dipped in each of the coloring compositions prepared in the foregoing Examples and Comparative Examples for 20 seconds, then the amount of the composition adhered to the taffeta was controlled to a level corresponding to a rate of pickup of 80 ±2% according to the padding method, the colored taffeta was dried at 120°C for one minute and the fibers thus colored were visually inspected for the uniformity of the coloration thereof. O- The whole surface was uniformly colored; A- There were observed the presence of some small color spots; X : There was observed the presence of distinct color spots. (Test for the Confirmation of Aesthetic Property) Fabrics subjected to the coloring treatment in the foregoing 'Mesh-Permeation Test 2" and "Color Spots Test" were inspected for the aesthetic properties which were evaluated on the basis of the difference in the feehng upon the touch with the fingers between the fabrics before (raw fabrics) and after the coloring treatment. O- There was not observed any difference; A- There was observed slightly hard aesthetic properties; X : There was observed distinct change in the aesthetic properties. (Test for Fastness to Rubbing) Fabrics subjected to the coloring treatment in the foregoing "Mesh-Permeation Test 2" and "Color Spots Test" were inspected for the fastness to rubbing according to the testing method specified in JIS L 0849 and the results were judged on the basis of the evaluation standards hkewise specified therein. The evaluation standards specified in JIS L 0801-9 (Determination of Fastness to dyeing) were adopted herein as the evaluation standards for the dry and wet fastness to rubbing. The results thus obtained are summarized in the following Tables 1 (dye transfer technique) and 2 (dip dyeing technique). The materials 1 to 14 used are as follows^ i: PRINTEX 25 (black pigment available from Degussa Japan Co., Ltd.); 2' SMA-1000 (a dispersant resin available from Arakawa Chemical Industry Co., Ltd.); 3: Acetylene Glycol 104H (a wetting agent available from Nisshin Chemical Industry Co., Ltd.); 4: Naphthol Red (a red pigment available fi:om Fuji Dyestuff Co., Ltd.); 5: PLUSCOAT Z"221 (a dispersant resin available from GO Applied Chemical Industry Co., Ltd.); 6- Ryudye-W Black RC cone (an aqueous dispersion of a black pigment available from Dainippon Ink and Chemicals Inc.); 7- New Lacqutimine Standard Red FL3G cone (an aqueous dispersion of a red pigment available from Dainippon Ink and Chemicals Inc.); 8: PEGASOL 3040 (mineral spirit available from Exxon Mobil Corporation); 9: Hi-ol PKC-500 (an emulsifying agent available from HAYASHI Chemical Industry Co., Ltd.); 10- Bismol ET-55 (an emulsifying-thickening agent available from Toho Chemical Industry Co., Ltd.); li; U-205 (urethane binder emulsion available from Alberding Company; Tg 12: MATSUMISOL MR-50-1 (acryl binder emulsion available from Matsui Dyestuff Industry Co., Ltd.; Tg 13: NK Binder 1753 (acryl biader emulsion available from Shin Nakamura Chemical Industry Co., Ltd.; Tg = 32°C); 14: A 10% aqueous solution of xanthane gum (thickening agent 1 available from SANSHOCo.,Ltd.). It has been confirmed, from the results listed in the foregoing Tables 1 and 2, that the colored fibrous structures prepared in Examples 1 to 4 according to the present invention are excellent in the uniform coloring ability, the aesthetic properties and the fastness to rubbing as compared with those observed for the colored fibrous structures prepared in Comparative Examples 1 to 3. The colored fibrous structure of Comparative Example 1 corresponds to one colored using the same coloring composition of Example 1 except that the pigment particles used have a large average particle size and it is recognized that the colored fibrous structure is inferior, to the article of Example 1, in the uniform coloring abihty, the aesthetic properties and the fastness to rubbing. The colored fibrous structure of Comparative Example 2 corresponds to one colored using the same coloring composition of Example 2 except that the pigment particles used have a large average particle size and it is recognized that the colored fibrous structure is inferior in the uniform coloring ability, the aesthetic properties and the fastness to rubbing. The colored fibrous structure of Comparative Example 3 corresponds to one colored using the same coloring composition of Example 4 except that the binder particles used have a large average particle size and it is recognized that the colored fibrous structure is inferior, to the article of Example 4, in the leakage characteristics, the uniform coloring abihty, the color spot-formation, the aesthetic properties and the fastness to rubbing. What is claimed is- 1. A coloring composition comprising pigment particles whose average particle size is not more than 200nm and binder polymer particles. 2. The coloring composition as set forth in claim 1, wherein the composition comprises binder poljmier particles having an average particle size of not more than 200nm. 3. The coloring composition as set forth in claim 1, wherein the pigment particles are ones subjected to a hydrophihzation treatment. 4. The coloring composition as set forth in claim 3, wherein the pigment particles are hydrophilized with a dispersant consisting of a surfactant and a water-soluble polymer. 5. The coloring composition as set forth in claim 4, wherein the pigment particles are ones each comprising at least one hydrophilic group selected from the group consisting of hydroxyl group, carboxyl group and amino group. 6. The coloring composition as set forth in claim 2, wherein the binder polymer particles have a Tg value (glass transition point) of not higher than 10°C and an average particle size ranging from lOnm to lOOnm. 7. The coloring composition as set forth in claim 5, wherein the average particle size of the pigment particles falls within the range of from lOnm to lOOnm. 8. The coloring composition as set forth in claim 7, wherein the composition has a viscosity ranging from 1000 to 200,000mPa' s. 9. The coloring composition as set forth in claim 7, wherein the composition has a viscosity ranging from 10 to l,000mPa-s. 10. A method for the dye transfer-coloration of a fibrous structure characterized in that it uses the coloring composition as set forth in claim 8. 11. The method for the dye transfer-coloration as set forth in claim 10, wherein the fibrous structure is dye transfer-colored according to the silk screen printing technique, while using a high mesh screen having a pore size of not less than 120 mesh and a rubber squeegee having a Shore hardness ranging from 40 to 90 degrees. 12. A method for the dip-coloration of a fibrous structure comprising using the coloring composition as set forth in claim 9. 13. The method for the dip-coloration as set forth in claim 12, wherein the rate of pick-up falls within the range of from 50 to 90%, 14. An article colored with a coloring composition as set forth in any one of claims 1 to 9. 15. The article as set forth in claim 14, wherein it is a fibrous structure.

Full Text

SPECIFICATION Coloring Composition and Coloring Method
Technical Field
The present invention relates to a coloring composition, a coloring method and an article colored with the coloring composition and more partictdarly to a coloring composition which permits the clear and uniform coloration of a substance to be colored such as a fibrous structure, a method for coloring such substance and an article colored with the coloring composition.
Background Art
As techniques for coloring articles (a substance to be colored), for instance, fibrous structures such as yams or threads, cloths, woven goods, knitted goods, and nonwoven fabrics, there have conventionally been tried a variety of coloring methods such as the dip dyeing technique in which a fibrous stmicture is dipped in a coloring composition, and the printing technique in which a fibrous structure is colored using a transfer-controlling plate such as a silk screen printing plate, a stencil printing plate, a rehef printing plate, an intaglio printing plate, and a lithographic printing plate.
In the dip dyeing technique, a dye is used as a coloring dye, a fibrous structure is dipped in such a dye composition under heating and pressurizing conditions to thus make the dye penetrate into the fibrous structure, or such a fibrous structure is stirred and kneaded in the dye composition to uniformly adhere the dye to the structure and to thus prevent the formation of any color spot and/or the occurrence of any insufficient coloration. After the completion of the coloring step, the colored fibrous structure is washed with water or an aqueous solvent to remove any excess coloring component and to thus give a colored fibrous structure having good fastness of color without impairing the aesthetic property of the structure.

There have been proposed various kinds of coloring dye compositions suitably used for coloring naturally occurring fibrous materials such as those obtained from cotton, hemp, silk, and wool fibers as well as synthetic fibrous materials such as those made of polyester, acrylic, rayon and nylon fibers, while appropriately selecting the kinds of dyes used as dyestviffs for coloration and they have widely been used for the coloration of a variety of fibrous materials such as those hsted above. However, this technique suffers from such a drawback that a specific dye should be properly selected depending on each particvdar fibrous material for the coloration since the technique makes use of a dye as a dyestuff for coloration. In particular, when coloring a mixed fibrous material comprising at least two different fibrous materials, this technique should use a plurality of coloring compositions or a plurahty of coloring steps.
Moreover, the technique requires, in the coloring and/or washing processes, the use of a large quantity of energy and a large amount of industrial water for the heating, pressurizing, stirring and washing steps. This in turn leads to the discharge of a large amount of waste water and therefore, there has been desired for the development of a novel coloring method and a novel coloring composition in the fight of, for instance, the achievement of a high energy efficiency, the effective use of water resources and the prevention of any environmental pollution.
In the printing (or dye transfer) technique, the transfer-controlling plate can be used for controUing the amount of the dye to be adhered and the area to which the dye is adhered when adheiing a coloring composition to a fibrous structure and accordingly, this technique is an excellent coloring method which permits the high quahty and highly precise coloration of, for instance, fine designs and patterns, pictorial symbols, dabbed patterns and/or gradated patterns. The coloring composition used in the dye trainsfer technique must be prepared so as to have such a viscosity that the transfer-controUing plate can normally show its function and in case of, for instance, a silk screen printing plate, the viscosity of the composition should be controlled to such a level that the composition does not

cause any leakage through the mesh of the screen. The coloring agent used in this technique may be either dyes or pigments.
When using a dye, the colored fibrous structure is washed with water or an aqueous solvent, after the coloring step, to remove any excess coloring component and to thus give a colored fibrous structure having good fastness of color without impairing the aesthetic property of the structure, like the dip dyeing technique. There have been proposed various kinds of coloring dye compositions suitably used for coloring naturally occurring fibrous materials such as those obtained from cotton, hemp, silk, and wool fibers as well as synthetic fibrous materials such as those made of polyester, acryUc, rayon and nylon fibers, while appropriately selecting the kinds of dyes to be used and they have widely been used for the coloration of a variety of fibrous materials such as those hsted above.
On the other hand, when using a pigment, a binder shoiold be used for firmly adhering the pigment per se to a fibrous structure and accordingly, there has been used a coloring composition simultaneously comprising a polymer compound as a binder.
However, the dye transfer technique, which makes use of a coloring composition containing a dye, likewise suffers from such a drawback that a specific dye should be properly selected depending on each particular fibrous material for the coloration since the technique makes use of a dye as a dyestuff for coloration. Like the dip dyeing technique. In particular, when coloring a mixed fibrous material comprising at least two different fibrous materials, this technique should use a plurahty of coloring compositions or a plurality of coloring steps.
Accordingly, this technique requires, in the coloring and/or washing processes, the use of a large quantity of energy and a large amount of industrial water for the heating, pressurizing, stirring and washing steps. This in turn leads to the discharge of a large amount of waste water. Therefore, there has likewise been desired for the development of a novel coloring method and a novel coloring

composition in the light of, for instance, the achievement of a high energy efficiency, the effective use of water resources and the prevention of any environmental pollution.
Moreover, the dye transfer technique, which makes use of a coloring composition containing a pigment, also suffers from drawbacks such that particles of the pigment and/or the polymer compound used as a binder are adhered to the surface of a transfer-controlling plate and this in turn results in the reduction of the amount of the composition adhered to the fibrous structure and the area thereof to be colored and that the pigment and/or the polymer compound adhered to the fibrous structure may reduce the aesthetic properties and flexibUity of the fibrous structure. For this reason, there has been desired for the development of a novel coloring composition.
Patent Document 1 discloses a coloring agent for use in the dip dyeing technique, whose particle size is not more than 0.5 /i m, a colored article obtained using the composition and a coloring method which makes use of the same. However, the coloring dyestuff used in this coloring agent is a disperse dye and accordingly, this method does not improve or eliminate the problems of the appropriate selection of the material for a fibrous structure due to the use of a dye; the requirement for the use of complicated steps; the requirement for large quantities of energy and industrial water; the delivery of a large quantity of waste water.
In addition, Patent Document 2 discloses an ink composition whose particulate materials as the components thereof have a particle size of not more than 10 jixa and a screen printing method which makes use of the ink, but this technique has not yet satisfactorily solved the problems concerning the impairment of the aesthetic properties and the flexibihty of the fibrous structure to be treated.
Patent Document 1- Japanese Un-Examined Patent PubHcation 2003-313454;
Patent Document 2* Japanese Un-Examined Patent Publication 2004-195697.

Disclosure of the Invention
Problems That the Invention is to Solve
Accordingly, it is an object of the present invention to provide a coloring composition which can eliminate the drawbacks associated with the foregoing conventional techniques and a coloring method which makes use of the composition.
It is another object of the present invention to provide a coloring composition which has a good color-developing ability and excellent fastness of color and which would permit the formation of a thin and uniform colored and coated layer on the surface of a fibrous structure without impairing the aesthetic properties of the fibrous structure.
It is still another object of the present invention to provide a coloring composition which has a high color-developing abihty is not accompanied by the formation of any color spot and which permits the coloration of any fibrous structure irrespective of the kinds of their materials, without causing the reduction of the aesthetic properties and flexibility of the fibrous structure.
It is a further object of the present invention to provide a method for coloring even a naiixed material using a single coloring composition and at a single step.
It is a still further object of the present invention to provide a method for coloring a fibrous structural material, which is qxxite simple, can ensure a high working efficiency, a high energy efficiency and quite effective use of water resources and which is free of any environmental pollution.
It is a stiU further object of the present invention to provide a coloring method which does not require the use of any washing step, requires the use of a reduced quantity of energy, provides only a small amount of waste water, ensures effective use of water resources and is free of any environmental pollution.
It is a still further object of the present invention to provide an article

colored by the foregoing coloring composition.
Means for the Solution of the Problems
The inventors of this invention have conducted various studies, have found that the foregoing objects of the present invention can be accomplished by the use of a pigment having a specific particle size as the dyestuff for the coloration and by adjusting the average particle size of the whole particles dispersed in a coloring composition including the pigment particles to a level of not more than 200 nm and have thus completed the present invention. According to the present invention, there are thus provided the following coloring composition and the following coloring method which makes use of the coloring composition:
1. A coloring composition comprising pigment particles whose average particle size is not more than 200nm and binder polymer particles.
2. The coloring composition as set forth in the foregoing item 1, wherein the composition comprises binder polymer particles having an average particle size of not more than 200nm.
3. The coloring composition as set forth in the foregoing item 1 or 2, wherein the pigment particles are ones subjected to a hydrophihzation treatment.
4. The coloring composition as set forth in any one of the foregoing items 1 to 3, wherein the pigment particles are hydrophilized with a dispersant consisting of a surfactant and a water-soluble polymer.
5. The coloring composition as set forth in the foregoing item 4, wherein the pigment particles are ones each comprising at least one hydrophilic group selected from the group consisting of hydroxyl group, carboxyl group and amino group.
6. The coloring composition as set forth in any one of the foregoing items 2 to 5, wherein the binder polymer particles have a Tg value (glass transition point) of not higher than 10°C and an average particle size ranging from lOnm to lOOnm.
7. The coloring composition as set forth in any one of the foregoing items 1 to 6, wherein the average particle size of the pigment particles falls within the range of

from lOnm to lOOnm.
8. The coloring composition as set forth in any one of the foregoing items 1 to 7, wherein the composition has a viscosity ranging from 1000 to 200,000mPa- s.
9. The coloring composition as set forth in any one of the foregoing items 1 to 7, wherein the composition has a viscosity ranging from 10 to l,000mPa-s.
10. A method for the dye transfer-coloration of a fibrous structure characterized in that it uses the coloring composition as set forth in the foregoing item 8.
11. The method for the dye transfer-coloration as set forth in the foregoing item 10, wherein the fibrous structure is dye transfer-colored according to the silk screen printing technique, while using a high mesh screen having a mesh size of not less than 120 mesh and a rubber squeegee having a Shore hardness ranging from 40 to 90 degrees.
12. A method for the dip-coloration of a fibrous structure comprising using the coloring composition as set forth in the foregoing item 9.
13. The method for the dip-coloration as set forth in the foregoing item 12, wherein the rate of pickup falls within the range of from 50 to 90%.
14. An article colored with a coloring composition as set forth in any one of the foregoing items 1 to 9.
15. The article as set forth in the foregoing item 14, wherein it is a fibrous
structure.
Effects of the Invention
The coloring composition and coloring method of the present invention make use of pigment particles, as a dyestuff for coloration, whose average particle size is not more than 200nm and polymer particles, as a binder, preferably having an average particle size of not more than 200nm and therefore, they can form a thin and uniform colored and coated layer on the surface of a fibrous structure \^dthout impairing the aesthetic properties of the fibrous structure; they can ensure a good color-developing ability and excellent fastness of color; they permit

)

the coloration of even a mixed material using a single coloring composition and by a single coloring step; they can further ensure a high working efficiency, a high energy efficiency and quite effective use of water resources and they are substantially free of any environmental pollution.
It is considered that the following are the reasons why the coloring composition and coloring method of the present invention are excellent as compared with the conventional ones-
The conventional fiber-coloring composition which makes use of a pigment undergoes adhesion to the fibrous structure, forms a thick color-developing coated layer since the particles of the pigment and a binder poljoner used therein have a large particle size. Accordingly, it has not provided any clear color-development and, in turn, any colored fibrous structure having good aesthetic properties.
On the other hand, the coloring composition and coloring method of the present invention make use of a pigment and a polymer binder, which have been finely pulverized to a specific particle size. Accordingly, they can form a thinner colored, coated layer, while the aesthetic properties of the resulting colored fibrous structure can be maintained or even improved, the generation of voids in the coated layer can be hmited to a lowest possible level, the resulting article has an improved fastness of color and they also ensure a clear color-development.
Best Mode for Carrying Out the Invention
Various modes for carrying out the present invention will hereunder be described in more detail.
In the present invention, the term "fibrous structure" means yarns or threads, cloths, woven goods, knitted goods, nonwoven fabrics, paper, plates, leather and other sheet-like products, as well as articles prepared from these products, which are made of natural fibers, synthetic fibers, semi-synthetic fibers or mixture thereof.
The coloring composition of the present invention is characterized in that it

uses a pigment whose average particle size is not more than 200nm as a dyestuff component for coloration and the composition is preferably characterized in that it comprises polymer particles having an average particle size of not more than 200nm as a binder component.
As the dyestuff component for coloration used in the coloring composition of the present invention, usable herein include aU of the inorganic and organic pigments which can be dispersed in water and an aqueous solvent and have chromatic colors. Moreover, it is also possible to use pseudo-pigments obtained by pigmenting resin emulsions with dyes or the like.
Such inorganic pigments may be, for instance, metal powder and powdery metal-containing compounds, while such organic pigments may be, for instance, azo lake pigments, insoluble azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dye lake pigments, nitro pigments, and nitroso pigments.
More specifically, examples of pigments usable herein include inorganic pigments, for instance, carbon black such as channel black, furnace black and thermal black, titanium black, iron black, lead black, copper-chromium black, cobalt black, red iron oxide, chromium oxide, cobalt blue, yellow iron oxide, viridian, cadmium yellow, vermihon, cadmium red, lead yellow, molybdate orange, zinc chromate, strontium chromate, ultramarine blue, barite powder, iron blue, manganese violet, aluminum powder, and brass powder; and organic pigments such as aniline black, perylene black, cyanine black, pseudo-pigments obtained by pigmenting resin emulsions with black dyes, C.I. Pigment Blue 1, C.I. Pigment Blue 15, C.I. Pigment Blue 17, C.I. Pigment Blue 27, C.I. Pigment Red 5, C.I. Pigment Red 22, C.I. Pigment Red 38, C.I. Pigment Red 48, C.I. Pigment Red 49, CI. Pigment Red 53, C.I. Pigment Red 57, CI. Pigment Red 81, CI. Pigment Red 104, CI. Pigment Red 146, CI. Pigment Red 245, CI. Pigment Yellow 1, CI. Pigment Yellow 3, CI. Pigment Yellow 4, CI. Pigment Yellow 12, CI. Pigment Yellow 13, CI. Pigment Yellow 14, CI. Pigment Yellow 17, CI. Pigment Yellow 34,

CI. Pigment Yellow 55, C.I. Pigment Yellow 74, C.I. Pigment YeUow 83, C.I. Pigment YeUow 95, C.I. Pigment Yellow 166, CI. Pigment Yellow 167, CI. Pigment Orange 5, CI. Pigment Orange 13, CI. Pigment Orange 16, CI. Pigment Violet 1, CL Pigment Violet 3, CI. Pigment Violet 19, CI. Pigment Violet 23, CI. Pigment Violet 50, and CL Pigment Green 7, In the present invention, the foregoing pigments may be used alone or in any combination of at least two of
them.
The average particle size of the pigment particles present in the coloring composition of the present invention is not more than 200nm and preferably not more than lOOnm. This is because if the coloring composition contains pigment particles whose average particle size exceeds 200nm, the surface roughness of the resulting colored fibrous structure increases and this accordingly leads to the increase of the frictional resistance and the corresponding reduction of the fastness to rubbing. On the other hand, if the coloring composition contains pigment particles whose average particle size is less than lOnm, the resulting coloring composition is Hable to cause the reduction of, for instance, the color density developed and the weatherabihty. Therefore, the average particle size of the pigment particles used in the present invention preferably ranges from 10 to 200nm and more preferably 20 to lOOnm.
As the means for controUing the average particle size of the pigment particles, usable herein includes, for instance, a method comprising the steps of adding, to the foregoing pigment, water and an aqueous solvent and optionally a wetting agent, a moisturizing agent, a dispersion stabilizer or the Like and then blending them using a shear force-applying tj^e dispersion device currently used in this field. For instance, the foregoing mixture is processed using, for instance, a stirring type dissolver, a homomixer, a Henschel mixer, a medium-type ball mill, a sand mill, an attritor, a paint-shaker, a medium-less type three-roll or five-roU mill, a jet mill, a water-jet mill or an ultrasonic dispersion device for a predetermined period of time to thus give pigment particles having an intended

average particle size.
In addition, desired pigment particles having a predetermined average particle size can more certainly be prepared when by pulverizing and dispersing the pigment in a dispersion device and then optionally removing coarse particles and extremely fine particles present in the resvdting pigment particles. The pigment particles other than those having a desired particle size may be removed by, for instance, the static settling technique, the centrifiigal sedimentation technique, or the removal through filtration.
The pigment particles used in the present invention are quite fine and accordingly, they may again undergo agglomeration due to any external factor or upon the coloring process to thus impair the desire quality of the coloring composition. To prevent such re-agglomeration of the pigment particles, it is preferred to subject the surface of the pigment particles to a hydrophihzation treatment in advance.
Examples of such hydrophilization treatments are those comprising the step of imparting, to the surface of pigment particles, hydrophihc groups such as hydroxyl, carboxyl, and/or amino group through the treatment of the pigment particles with a dispersing agent containing a surfactant and/or a water-soluble polymer to thus improve the stability of the particles. Examples of such surfactants usable herein are anionic ones such as alkyl carboxyhc acid esters, alkyl-sulfuric acid esters and alkyl-phosphoric acid esters; cationic ones such as aliphatic ammonium salts; and nonionic ones such as alkyl ethers, fatty acid ester ethers and sorbitan fatty acid esters. In addition, examples of the foregoing water-soluble polymers usable herein include polymeric dispersing agents such as poljrvinyl pyrrohdone, polyvinyl alcohols, acrylics (such as low molecular weight polyacrylic acids and polyCmethacryhc acids)), poly(maleic adds), copolymers of styrene with acryhc acid, methacryhc acid or the hke, poly amides and rosin-modified maleic acids.
Furthermore, it is also possible to hydrophilize the surface of pigment

particles using a treatment with an alkali such as sodium hydroxide, a treatment with an oxidizing agent such as chromic acid, or a topochemical treatment such as the low temperature plasma treatment.
Among the hydrophihc groups which can he imparted to the surface of the pigment particles, hydroxyl and carboxyl groups are particularly preferred since they may cause a cross-hnking reaction with hinder polymer molecules and a crosslinking agent during the coloration of a fibrous structure and this may in Uxm result in the effect of improving the fastness of the color.
The content of the pigment particles in the coloring composition of the present invention preferably ranges from 0.1 to 15% by mass and more preferably 0.5 to 10% by mass based on the total mass of the coloring composition. This is because if the content thereof is less than 0.1% by mass, there is observed such a tendency that the resulting composition does not show any satisfactory color development, while if it exceeds 15% by mass, the resulting coloring composition has such a tendency that the fastness thereof to rubbing is reduced.
The binder polymer used in the present invention should be one capable of being dispersed in water and an aqueous solvent in the form of fine particles preferably having an average particle size of not more than 200nm and more preferably not more than lOOnm. On the other hand, if the coloring composition contains a binder polymer whose average particle size exceeds 200nm, there may be observed the following tendency- the thickness of the coated layer formed by the binder polymer increases and this in turn leads to the deterioration of the aesthetic properties of the fibrous structure colored by the composition and the ability of the binder polymer to bind the pigment particles is reduced and this accordingly results in the reduction of the fastness thereof to rubbing. On the other hand, if binder polymer particles having an average particle size of less than lOnm are present in the coloring composition, there may be such a tendency that the liquid coloring composition becomes unstable due to the agglomeration of such fine particles. For this reason, the average particle size of the binder particles

used in the present invention preferably ranges from 10 to 200nm and more preferably 20 to lOOnm. In particular, it is quite preferred to use the binder polymer particles, whose average particle size is controlled in such a manner that it falls within the range of from 10 to lOOnm, since the use thereof permits the formation of a micro-coat as a coated layer formed from the binder polymer, while maintaining the aesthetic properties of the fibrous structure and the use likewise permits the improvement of the abihty of the binder polymer to bind the pigment
particles.
The binder polymer used in the present invention desirably has a glass transition temperature of preferably not higher than 10°C and more preferably not higher than 5°C. If the glass transition temperature of the binder polymer exceeds 10°C, the binder polymer insufficiently forms a coated film when the coloring method of the present invention is appHed to a fibrous structure in such a working environment maintained at room temperature (20'C± 10°C) and a large number of voids are formed in the resulting film. There is observed such a tendency that these voids remains in the film even after the heat-treatment thereof and this accordingly reduces the strength of the coated layer made of the binder polymer. On the other hand, if the glass transition temperature of the binder polymer is less than 10°C, the binder polymer can form a uniform film even at room temperature to thus prevent any reduction of the strength of the resulting film. The binder polymer used in the present invention is not restricted to any specific one inasmuch as it may satisfy the foregoing reqviirements and examples thereof include easily available and commonly used ones such as acrylic polymers, acryhc monomer-styrene copolymer, acryhc monomer-urethame copolymers, acryHc monomer-maleic acid copolymers, acryhc monomer-butadiene copolymers, acryhc monomer-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, polyurethanes and poly olefins.
The binder polymer used in the present invention may be in the form of, for instance, an emulsion or a dispersion.

The content of the binder poljrmer particles in the coloring composition of the present invention preferably ranges from 0.5 to 20% by mass and more preferably 1 to 10% by mass based on the total mass of the coloring composition. This is because if the content thereof is less than 0.5% by mass, there is observed such a tendency that the binder polymer does not show its abihty as a binder and the resulting composition shows a reduced fastness to rubbing, whUe if it exceeds 20% by mass, the resulting coloring composition has such a tendency that the aesthetic properties of the fibrous structure processed with the composition are impaired.
The coloring composition of the present invention can be used for the coloration of a variety of articles. Examples of such articles are fibrous structures such as yarns or threads, cloths, woven goods, knitted goods, nonwoven fabrics, paper, plates, and leather. The coloring methods particularly preferably used for coloring fibrous structures include, for instance, the dye transfer technique and the dip dyeing technique.
When coloring a fibrous structure according to the dye transfer technique, the coloring composition used in the technique should have such a viscosity that the transfer-controUing plate can normally show its function. For instance, in case where a silk screen printing plate is used, the viscosity of the composition should be controlled to such a level that the composition does not cause any leakage through the mesh of the screen used.
For instance, when using a silk screen printing plate having a large pore size on the order of 60 mesh, filaments each having a diameter of 83 M m are usually used, the screen has a rate of opening of 65% and a pore size of 340 jx m and accordingly, the composition should have a viscosity at which the coloring agent does not permeate into the screen even at a penetration volume of 55 cm^/m^.
The coloring composition of the present invention comprises pigment particles and binder polymer particles, having a quite small particle size and

therefore, the viscosity thereof should be controlled to a level of not less than 5,000mPa"S and preferably not less than 20,000mPa'S. However, if the viscosity thereof is too high on the order of higher than 200,000mPa'S, the meshes of the screen printing plate are plugged with the coloring composition and accordingly, the coloration of a fibrous structure is liable to be insufficient. For this reason, when using a silk screen printing plate having a large pore size on the order of 60 mesh, the coloring composition used should have a viscosity preferably ranging from 5,000 to 200,000mPa-s and more preferably 20,000 to 100,000mPa-s.
On the other hand, when using a silk screen printing plate having a small pore size on the order of 120 mesh, filaments each having a diameter ranging from 48 to 83 M m are usually used, the screen has a rate of opening of 49% and a pore size of 152 /i m and accordingly, the composition used should have a viscosity at which the coloring composition does not permeate into the screen even at a penetration volume of 39 cm^/m^ and which also permits the appropriate passage of the composition through the screen mesh when appljdng a pressure with a squeegee. To prevent the permeation of any coloring composition through the screen, the viscosity of the composition is desirably controlled to a level of not less than 3,000mPa'S and preferably not less than 15,000mPa'S. However, if the viscosity thereof exceeds 150,000mPa-s, when pressurizing the screen with a squeegee, the meshes of the screen printing plate are plugged with the coloring composition and accordingly, the coloration of a fibrous structure is liable to be insufficient, because of the extremely high viscosity of the composition. Accordingly, when using a silk screen printing plate having a small pore size on the order of 120 mesh, the coloring composition used should have a viscosity preferably ranging from 3,000 to 150,000mPa-s and more preferably 15,000 to 80,000mPa-s.
When using a silk screen printing plate having a pore size of 230 mesh for the purpose of accomplishing the high quahty and high precision dye transfer coloration, filaments each having a diameter ranging from 48 to 67 M m are

usually used, the screen has a rate of opening of 28% and a pore size o£ 65 iixn and accordingly, the coloring composition used should have a viscosity at which the composition does not permeate into the screen even at a penetration volume of 22 cm^/m^ and which also permits the appropriate passage of the composition through the screen mesh when applying a pressure with a squeegee. To prevent the permeation of any coloring composition through the screen, the viscosity of the composition is desirably controlled to a level of not less than l,000mPa-s and preferably not less than 2,000mPa-s. However, if the viscosity thereof exceeds 120,OOOmPa'S, when pressurizing the screen with a squeegee, the meshes of the screen printing plate are plugged with the coloring composition and accordingly, the coloration of a fibrous structure is Hable to be insufficient, because of the extremely high viscosity of the composition. Accordingly, when using a silk screen printing plate having a finer pore size on the order of 230 mesh, the coloring composition used should have a viscosity preferably ranging from 1,000 to 120,000mPa-s and more preferably 2,000 to 70,000mPa'S.
When coloring, in this way, fibrous structures using the coloring composition of the present invention according to the dye transfer technique, the viscosity of the coloring composition should be adjusted while taking into consideration the mesh size, pore size and penetration volume of the silk screen printing plate. Thus, high quality and high precision pictorial symbols, dabbed patterns and/or gradated patterns can be colored at high resolution.
The squeegee used in the coloring method according to the present invention should be one which can apply a desired pressure to the coloring composition present on the silk screen printing plate, can satisfactorily make the composition pass through the openings of the screen printing plate and can appropriately scratch off the unnecessary coloring composition from the silk screen and accordingly, the squeegee should have appropriate elastic characteristics. If the squeegee has a Shore hardness of not more than 35 degrees, the resulting squeegee is insufficient in its strength and it may immediately be

worn out, while if the Shore hardness thereof is higher than 91 degrees, the resulting squeegee has insufficient elastic characteristics and accordingly, the squeegee does not serve to appropriately scratch off, from the silk screen, the unnecessary coloring composition. For this reason, the hardness of the squeegee used in the coloring method of the present invention more preferably ranges from 40 to 80 degrees and the squeegee would have highly satisfied physical properties and excellent durabihty inasmuch as the hardness thereof falls within the range specified above. The usual elastic molded articles and resins commercially available can be used as the material for forming such a squeegee without any restriction insofar as they satisfy the foregoing requirement for the physical properties or the Shore hardness specified above. Specific examples thereof are acrylic rubber, acryhc urethane rubber, acryhc nitrile rubber, acrylic butadiene rubber (acryhc acid or methacryhc acid-butadiene rubber), urethane rubber, butadiene rubber, butyl rubber, NBR (acrylonitrile-butadiene rubber), epoxy elastomers and fluororubber.
Various kinds of thickening agents can be used for controlling the viscosity of the coloring composition according to the present invention. Such a thickening agent may be, for instance, at least one member selected from the group consisting of synthetic polymers, cellulose materials and polysaccharides and terpene emulsions, which naay be used alone or in any combination of at least two of them.
Specific examples of the foregoing synthetic poljnners are polyacryhc acids, polyvinyl alcohol, polyethylene oxide, polyAdnyl pyrrolidone, polyvinyl methyl ether, and polyacrylamide. Specific examples of cellulose materials are ethyl cellulose, methyl cellulose, hydroxymethyl cellulose, and carboxymethyl cellulose. Specific examples of the foregoing polysaccharides are xanthane gum, guar gum, casein, gum arabic, gelatin, carrageenan, alginic acid, tragacanth gum, locust bean gum, and pectin. Specific examples of the foregoing terpene emulsions include mousse-like emulsions each obtained by emulsifying a mixture of mineral

terpene and water with a nonionic surfactant.
In case where a fibrous structure is colored using the coloring composition of the present invention according to the dip dyeing technique, the viscosity of the coloring composition should be controlled so that the fibrous structure is wetted with the coloring composition to thus stably adhere the pigment and the binder poljnner to the fibrous structure. In particular, if the viscosity of the composition is too low and when the pigment as the dyesttxff for the coloration is in the fine particulate state, the pigment adhered to the fibrous structure may migrate from the course area to the dense portion of the structure due to the capillary phenomenon thereof when drjong the structure provided thereon with the coloring composition adhered thereto and this in turn leads to the formation of color spots and any uniformly colored product cannot be obtained at all. For this reason, the viscosity of the composition is preferably adjusted to a level of not less than lOmPa-s. However, when the viscosity of the coloring composition exceeds lOOOmPa-s, the composition would hardly penetrates into the fibrous structure. Therefore, when coloring the fibrous structure according to the dip dyeing technique, the coloring composition of the present invention preferably has a viscosity ranging from 10 to lOOOmPa-s, and more preferably 20 to 500mPa-s.
The use of the coloring composition whose viscosity is adjusted to a level falling within the range specified above permits the formation of a satisfactorily colored fibrous structure according to the dip dyeing technique.
When coloring a fibrous structure with the coloring composition of the present invention according to the dip dyeing technique, the aesthetic properties and color-developing ability of the structure may variously vary depending on the amount of the coloring composition adhered thereto. Accordingly, the rate of pickup of the coloring composition (the adhered amount (by mass) of the composition (prior to drjdng) based on the amount (lOO parts by mass) of the fibrous structure) preferably ranges from 50 to 91% and more preferably 60 to 80%. If the rate of pickup is less than 50%, the adhered amount of the composition

is too low to give a colored product having a satisfactory hue corresponding to the sufficient coloration, while if it exceeds 91%, the adhered amoxmt of the composition is too high and this accordingly leads to the formation of a colored fibrous structure provided with an extremely thick coated layer and having impaired aesthetic properties. Thus, the use of the coloring composition of the present invention whose rate of pickup is adjusted to a level specified above permits the formation of a colored fibrous structure excellent in the color-developing ability, the aesthetic properties and the fastness of color.
In the fibrous structures colored using the coloring composition of the present invention according to the dip dyeing technique and the dye transfer technique, the pigment as the coloring dyestxiff is held on the surface of the fibers preferably by the action of the polymer biader and accordingly, the method of the invention does not require the use of any additional step for removing, for instance, any excess coloring agent, any sizing agent and any additive through washing with water after the coloration with the coloring composition and the subsequent drying operation. Moreover, the coloring method of the present invention using the coloring composition of the present invention does not require the selection of any appropriate dye suitably used for each particular fibrous material and the control of heating, pressurizing and stirring conditions for properly making the dye penetrate into the fibrous structure. Accordingly, the coloring method of the present invention permits the coloration of even a mixed material using a single coloring composition and a single step for coloration and accordingly, it can be said that the coloring method of the present invention is an excellent coloring method since it is excellent in the working efficiency and the energy efficiency, and it permits the effective use of the water resources and it is free of any environmental pollution.
The coloring composition of the present invention uses, as the solvent, water (for instance, tap water, distilled water, purified water, deionized water, pure water and deep sea water). In addition to water, however, it is also preferred

to use an aqueous medium other than water having a polar group which makes the medium compatible with water, which can impart water retention characteristics to the resulting composition and improve the stabihty of the pigment and the binder polymer. Examples of such aqueous mediums are methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, ethylene glycol monomethyl ether, glycerin, and pyrrohdone. In addition to these aqueous mediums, usable herein also include, for instance, non-aqueous solvents such as hquid paraffin, mineral oils and industrial gasoline, insofar as they can be blended with water or dispersed therein through the use of, for instance, an emulsifying agent. These solvents may be used alone or in any combination.
The content of water in the coloring composition of the present invention preferably ranges from 10 to 90% by mass and more preferably 30 to 80% by mass.
When the binder polymer is used alone in the coloring composition of the present invention, the resulting film may sometimes be insufficient in the strength and fastness thereof. In this case, the fastness of the resulting film can be improved by the incorporation, into the coloring composition, of a crossHnking agent which can undergo a crosshnking reaction with, for instance, hydroxyl and/or carboxyl groups present in the pigment and the binder polymer.
In this respect, the following crossHnking reactions can be used- the dehydration condensation reaction of methylol groups with hydroxyl groups; the epoxy ring-opening polymerization reaction of glycidyl groups with hydroxyl groups; the urethane-forming reaction of isocyanate groups with hydroxyl and/or carboxyl groups; the amide ester-forming reaction of oxazoHne groups with carboxyl group; the carbamoylamide-forming and isourea-forming reaction of carbodiimide groups with hydroxyl and carboxyl groups; the condensation dehydration reaction of silanol groups with hydroxyl groups; the dehydration condensation reaction of metal alkoxide groups with hydroxyl groups; the melamine-condensation reaction of polj^unctional methylol groups with hydroxyl

groups; and the reduction dehydration reaction of diacetone acryiamide with hydrazide and hydroxyl groups. When incorporating these aqueous crosshnking agents into the coloring composition and then heating the restdting mixture, the hydroxyl and carboxyl groups of the pigment and/or the binder polymer undergo a crosshnking reaction with the crosshnking agents to form a three-dimensional network and as a result, the fastness of the resulting film may substantially be improved.
The content of the crosshnking agent in the coloring composition of the present invention preferably ranges from 0.1 to 5% by mass and more preferably 0.2 to 2.5% by mass.
The coloring composition of the present invention may further comprise, in addition to the foregoiug components, other optional additives commonly or widely used in the coloring composition in an amount which does not adversely affect the intended effects of the present invention, for instance, an antiseptic agent, an antifungal agent, a sequestering agent, a pH-adjusting agent, a lubricant, and/or a wetting agent.
Examples of such antiseptic and antifungal agents include phenols, sodium
omadine, sodium pentachlorophenol, l,2-benzisothiazohn-3-one,
2,3,5,6-tetrachloro-4-(methyl-sulfonyl) pyridine, sodium benzoate, alkah metal salts of benzoic acid, sorbitan fatty acid and dehydro-acetic acid, and benzimidazole type compounds.
Examples of such sequestering agent are benzotriazole, dicyclohexyl ammonium nitrite, di-isopropyl ammonium nitrite, tolyl triazole, and saponins.
Examples of the foregoing pH-adjusting agent include urea, aqueous ammonia, monoethanolamine, triethanolamine, aminomethyl propanol, alkah metal salts of phosphoric acid such as sodium tripolyphosphoate and alkah metal hydroxides such as sodium hydroxide.
Examples of the foregoing lubricants and wetting agents are polyalkylene glycol derivatives such as polyoxyethylene lauryl ether, alkah metal salts of fatty

acids, silicone oil emulsions, polyether-modified silicones such as polyethylene glycol adducts of dimethylene polysiloxane, poly(tetrafluoroethylene) powder, fluorochemical surfactants, fluorine-modified oils and acetylene glycol.
Examples
Then the present invention will be described in more detail with reference to the following Pigment-Preparation Examples, Examples and Comparative Examples, but the present invention is not restricted to these specific Examples at all.
Pigment-Preparation Example 1" Pigment-Preparation Example Using Paint Shaker (Pigment l):

There was dispensed each of the foregoing components in the amount specified above, the components thus dispensed were stirred in a dissolver to give a uniform dispersion and then the resulting formvdation was stirred in a paint shaker for 8 hours under such a condition that the bead-packing rate by volume was set at 60% to thus give Pigment 1. The average particle size of pigment particles included in the resulting product of this pigment-preparation example 1 was determined using NICOMP 380ZLS (available from NOZAKI Sangyo Co., Ltd.) and lOOnra polystyrene particles (3100A) and 300nm polystyrene particles (3300A), as reference materials, which were available from Duke Scientific Corporation and had been authorized by NIST (National Institute of Standards

and Technology) according to the laser-diffraction technique and as a result, it was found to be 90nm.
Pigment'Preparation Example 2- Pigment-Preparation Example Using Paint Shaker (Pigment 2):

There was dispensed each of the foregoing components in the amount specified above, the components thus dispensed were stirred in a dissolver to give a uniform dispersion and then the resulting formvdation was stirred in a paint shaker for 10 hours at a bead-packing rate by volume set at 60% to thus give Pigment 2. The average particle size of pigment particles included in the resulting product of this pigment-preparation example 2 was determined according to the laser-diffraction technique and as a result, it was found to be 80nm.
Comparative Pigment 1^ Pigment 3^ Ryudye-W Black RC cone (*6)
The average particle size of pigment particles included in this comparative pigment 1 was determined according to the laser-diffraction technique and as a result, it was found to be 2.2 M m.
Comparative Pigment 2- Pigment 4- New Lacqutimine Standard Red FL3G cone (*7)
The average particle size of pigment particles included in this comparative

pigment 2 was determined according to the laser-diffraction technique and as a result, it was found to be 760nm.
Stock Sizing Formulation i: Thickening Agent 2

There was dispensed each of the foregoing components in the amount specified above, the components thus dispensed were treated for the emulsification thereof using a homomixer to give a mousse-hke thickening agent and the latter was used as the thickening agent for the preparation of the products of the following Examples and Comparative Examples.
Examples 1 to 4 and Comparative Examples 1 to 3
Each coloring composition was prepared using the components hsted in the following Tables 1 and 2 according to the compositions likewise specified in these Tables and then fibrous structures were colored using these coloring compositions according to the coloring methods specified below. In this connection, there were evaluated the physical properties and the working properties during the coloring operations of the coloring compositions prepared in Examples and Comparative Examples and the aesthetic properties and the fastness to rubbing of the colored fibrous structures, according to the following evaluation methods=
(Method for Determining Average Particle Size)
Each of the coloring compositions prepared in the foregoing Examples and

Comparative Examples was diluted 100 times with deionized water and the average particle size of the pigment particles dispersed therein was determined using NICOMP 380ZLS (available from NOZAKI Sangyo Co., Ltd.) and lOOnm polystyrene particles (3100A) and 300nm polystyrene particles (3300A), as reference materials, which were available from Duke Scientific Corporation and had been authorized by NIST (National Institute of Standards and Technology) according to the laser-diffraction technique.
(Method for the Determination of Viscosity)
The viscosity of the coloring compositions prepared in the foregoing Examples and Comparative Examples was determined at 25°C and at 0.5 rpm using TV-30 type Viscometer^ Cone Plate t5T)e Standard Rotor (available from TOKI Sangyo Co., Ltd.).
(Mesh-Permeation Test l) (Dye transfer technique/Leakage characteristics)
Each of the coloring compositions prepared in the foregoing Examples and Comparative Examples was allowed to stand, for 4 hours, on a silk screen printing plate having a fine mesh size of 120 (TG-1200 available from MURAKAMI Screen Co., Ltd.) to thus examine the leakage of the coloring composition through the screen with the naked eyes.
O- There was not observed any leakage of the coloring composition; A: There was not observed any leakage of the coloring composition, but the liquid moiety thereof permeated through the screen; X: There was observed the leakage of the coloring composition.
(Mesh-Permeation Test 2) (Dye transfer technique/Uniformity of coloration)
Each of the coloring compositions prepared in the foregoing Examples and Comparative Examples was allowed to stand, for 10 minutes, on a silk screen printing plate having a fine mesh size of 120 (TG-1200 available from

MURAKAMI Screen Co., Ltd.) and then a solid pattern was printed on the whole surface of a polyester taffeta (available fi:om IROZOME Co., Ltd.) with each composition using a squeegee made of urethane rubber having a Shore hardness of 50 degrees according to the dye transfer technique, dried at 120°C for one minute and the fibers thus colored were visually inspected for the uniformity of the coloration thereof.
O- The whole surface was uniformly colored; A- There were observed the presence of some small voids; X: There was observed the presence of distinct un-colored area.
(Color Spots Test) (Dip dyeing technique/Uniformity of coloration)
A polyester taffeta (available from IROZOME Co., Ltd.) was dipped in each of the coloring compositions prepared in the foregoing Examples and Comparative Examples for 20 seconds, then the amount of the composition adhered to the taffeta was controlled to a level corresponding to a rate of pickup of 80 ±2% according to the padding method, the colored taffeta was dried at 120°C for one minute and the fibers thus colored were visually inspected for the uniformity of the coloration thereof.
O- The whole surface was uniformly colored; A- There were observed the presence of some small color spots; X : There was observed the presence of distinct color spots.
(Test for the Confirmation of Aesthetic Property)
Fabrics subjected to the coloring treatment in the foregoing 'Mesh-Permeation Test 2" and "Color Spots Test" were inspected for the aesthetic properties which were evaluated on the basis of the difference in the feehng upon the touch with the fingers between the fabrics before (raw fabrics) and after the coloring treatment.
O- There was not observed any difference; A- There was observed slightly hard

aesthetic properties; X : There was observed distinct change in the aesthetic properties.
(Test for Fastness to Rubbing)
Fabrics subjected to the coloring treatment in the foregoing "Mesh-Permeation Test 2" and "Color Spots Test" were inspected for the fastness to rubbing according to the testing method specified in JIS L 0849 and the results were judged on the basis of the evaluation standards hkewise specified therein. The evaluation standards specified in JIS L 0801-9 (Determination of Fastness to dyeing) were adopted herein as the evaluation standards for the dry and wet fastness to rubbing.
The results thus obtained are summarized in the following Tables 1 (dye transfer technique) and 2 (dip dyeing technique).

The materials *1 to *14 used are as follows^
*i: PRINTEX 25 (black pigment available from Degussa Japan Co., Ltd.);
*2' SMA-1000 (a dispersant resin available from Arakawa Chemical Industry Co.,
Ltd.);

*3: Acetylene Glycol 104H (a wetting agent available from Nisshin Chemical
Industry Co., Ltd.);
*4: Naphthol Red (a red pigment available fi:om Fuji Dyestuff Co., Ltd.);
*5: PLUSCOAT Z"221 (a dispersant resin available from GO Applied Chemical
Industry Co., Ltd.);
*6- Ryudye-W Black RC cone (an aqueous dispersion of a black pigment available
from Dainippon Ink and Chemicals Inc.);
*7- New Lacqutimine Standard Red FL3G cone (an aqueous dispersion of a red
pigment available from Dainippon Ink and Chemicals Inc.);
*8: PEGASOL 3040 (mineral spirit available from Exxon Mobil Corporation);
*9: Hi-ol PKC-500 (an emulsifying agent available from HAYASHI Chemical
Industry Co., Ltd.);
*10- Bismol ET-55 (an emulsifying-thickening agent available from Toho Chemical
Industry Co., Ltd.);
*li; U-205 (urethane binder emulsion available from Alberding Company;
Tg *12: MATSUMISOL MR-50-1 (acryl binder emulsion available from Matsui
Dyestuff Industry Co., Ltd.; Tg *13: NK Binder 1753 (acryl biader emulsion available from Shin Nakamura
Chemical Industry Co., Ltd.; Tg = 32°C);
*14: A 10% aqueous solution of xanthane gum (thickening agent 1 available from
SANSHOCo.,Ltd.).
It has been confirmed, from the results listed in the foregoing Tables 1 and 2, that the colored fibrous structures prepared in Examples 1 to 4 according to the present invention are excellent in the uniform coloring ability, the aesthetic properties and the fastness to rubbing as compared with those observed for the colored fibrous structures prepared in Comparative Examples 1 to 3.
The colored fibrous structure of Comparative Example 1 corresponds to one

colored using the same coloring composition of Example 1 except that the pigment particles used have a large average particle size and it is recognized that the colored fibrous structure is inferior, to the article of Example 1, in the uniform coloring abihty, the aesthetic properties and the fastness to rubbing.
The colored fibrous structure of Comparative Example 2 corresponds to one colored using the same coloring composition of Example 2 except that the pigment particles used have a large average particle size and it is recognized that the colored fibrous structure is inferior in the uniform coloring ability, the aesthetic properties and the fastness to rubbing.
The colored fibrous structure of Comparative Example 3 corresponds to one colored using the same coloring composition of Example 4 except that the binder particles used have a large average particle size and it is recognized that the colored fibrous structure is inferior, to the article of Example 4, in the leakage characteristics, the uniform coloring abihty, the color spot-formation, the aesthetic properties and the fastness to rubbing.

What is claimed is-
1. A coloring composition comprising pigment particles whose average particle size is not more than 200nm and binder polymer particles.
2. The coloring composition as set forth in claim 1, wherein the composition comprises binder poljmier particles having an average particle size of not more than 200nm.
3. The coloring composition as set forth in claim 1, wherein the pigment particles are ones subjected to a hydrophihzation treatment.
4. The coloring composition as set forth in claim 3, wherein the pigment particles are hydrophilized with a dispersant consisting of a surfactant and a water-soluble polymer.

5. The coloring composition as set forth in claim 4, wherein the pigment particles are ones each comprising at least one hydrophilic group selected from the group consisting of hydroxyl group, carboxyl group and amino group.
6. The coloring composition as set forth in claim 2, wherein the binder polymer particles have a Tg value (glass transition point) of not higher than 10°C and an average particle size ranging from lOnm to lOOnm.
7. The coloring composition as set forth in claim 5, wherein the average particle size of the pigment particles falls within the range of from lOnm to lOOnm.
8. The coloring composition as set forth in claim 7, wherein the composition has a viscosity ranging from 1000 to 200,000mPa' s.
9. The coloring composition as set forth in claim 7, wherein the composition has a viscosity ranging from 10 to l,000mPa-s.
10. A method for the dye transfer-coloration of a fibrous structure characterized in that it uses the coloring composition as set forth in claim 8.
11. The method for the dye transfer-coloration as set forth in claim 10, wherein the fibrous structure is dye transfer-colored according to the silk screen printing technique, while using a high mesh screen having a pore size of not less than 120

mesh and a rubber squeegee having a Shore hardness ranging from 40 to 90 degrees.
12. A method for the dip-coloration of a fibrous structure comprising using the coloring composition as set forth in claim 9.
13. The method for the dip-coloration as set forth in claim 12, wherein the rate of pick-up falls within the range of from 50 to 90%,
14. An article colored with a coloring composition as set forth in any one of claims 1 to 9.
15. The article as set forth in claim 14, wherein it is a fibrous structure.

Documents:

5208-CHENP-2007 AMENDED PAGES OF SPECIFICATION 19-08-2011.pdf

5208-CHENP-2007 AMENDED CLAIMS 19-08-2011.pdf

5208-chenp-2007 form-3 19-08-2011.pdf

5208-CHENP-2007 CORRESPONDENCE OTHERS 03-03-2011.pdf

5208-CHENP-2007 EXAMINATION REPORT REPLY RECEIVED 19-08-2011.pdf

5208-chenp-2007-abstract.pdf

5208-chenp-2007-claims.pdf

5208-chenp-2007-correspondnece-others.pdf

5208-chenp-2007-description(complete).pdf

5208-chenp-2007-form 1.pdf

5208-chenp-2007-form 18.pdf

5208-chenp-2007-form 3.pdf

5208-chenp-2007-form 5.pdf

5208-chenp-2007-pct.pdf

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Patent Number

250152

Indian Patent Application Number

5208/CHENP/2007

PG Journal Number

50/2011

Publication Date

16-Dec-2011

Grant Date

12-Dec-2011

Date of Filing

19-Nov-2007

Name of Patentee

MITSUBISHI PENCIL CO., LTD

Applicant Address

23-37, HIGASHIOHI 5-CHOME SHINAGAWA-KU TOKYO 140-8537

Inventors:

#	Inventor's Name	Inventor's Address
1	MIYAMOTO, MASARU	C/O YOKOHAMA OFFICE MITSUBISHI PENCIL CO., LTD 5-12, IRIE, 2-CHOME KANAGAWA-KU YOKOHAMA-SHI KANAGAWA 221-8550
2	KAMAGATA, TADASHI	C/O YOKOHAMA OFFICE MITSUBISHI PENCIL CO., LTD 5-12, IRIE, 2-CHOME KANAGAWA-KU YOKOHAMA-SHI KANAGAWA 221-8550

PCT International Classification Number

C08L 101/00

PCT International Application Number

PCT/JP06/308103

PCT International Filing date

2006-04-18

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2005-120196	2005-04-18	Japan