JP4635153B2 - Water-based emulsion type resin composition for fabric, water-based ink composition for fabric using the same, and use - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an aqueous emulsion resin composition, and more specifically, oil repellency that exhibits transfer resistance and coating coat properties on a fabric under hot press and has excellent washing resistance to the transfer or coating coat resin component. In addition, the present invention relates to an aqueous emulsion resin composition for fabrics that imparts functions such as antifouling properties and a functional fabric in which the aqueous emulsion resin composition is coated on a fabric under hot press.

  In addition, the present invention uses an aqueous emulsion resin composition that imparts functions such as oil repellency having anti-washing properties and antifouling properties, and further has a coloring function and is transferred under hot press. TECHNICAL FIELD The present invention relates to a water-based ink composition for fabrics that exhibits printability or transferability as an adhesive property, and a printed fabric on which a desired pattern and / or characters are printed or transferred by various printing methods or transfer methods. .

  A fabric made of natural fibers and / or synthetic fibers is coated and / or impregnated with various functional resins or various functional agents to provide functions such as waterproofness, water repellency, quick drying, antifouling properties, antistatic properties, etc. In recent years, the functions have been diversified, for example, functions such as wrinkle prevention, form stability, pollen adhesion, antibacterial deodorization, tobacco deodorization, and so on. Various functional fabrics that have been provided with multiple functions have been studied or put into practical use. In addition, it is also true that various technical measures for improving the washing resistance, durability, and fastness of the functional effects imparted to the fabric in this way have been studied or much anticipated.

  In addition, when transferring and / or impregnating such a functional resin or the like to the fabric, these functional resins may be transferred and / or transferred to the fabric as, for example, a functional colored resin component having a coloring function. Can be impregnated. Conventionally, such a functional colored resin component is transferred to and / or impregnated into a fabric and put into practical use as a fabric having a desired pattern and / or letters. That is, printed fabrics on which designs and / or characters are printed or transferred are widely used.

  Thus, for example, in [Patent Document 1], a main component is a fluoropolymer emulsion obtained by using an anion, a cation and a nonionic surfactant as an emulsifier in order to develop functions such as antifouling property and water repellency in a fabric. Furthermore, functional fabrics have been proposed in which an emulsion-type resin composition containing an acrylic resin or the like is applied to a woven fabric or a nonwoven fabric as a functional surface treatment agent.

  [Patent Document 2] describes a polyurethane resin solution as a resin composition that is applied to a woven or non-woven fabric of cellulose, polyester, nylon, etc. by a wet film forming method to impart a moisture permeable waterproof function to the fabric. In addition, a polyurethane resin composition for moisture permeable and waterproof fabrics in which oligomers having urea bonds and organopolysiloxane groups in the molecule or fine polymer particles having a particle size of 5 μm or less are dispersed is proposed.

  In addition, various impregnations such as conventionally known spray coating, dipping, spin coating and the like are performed to impart such a function to the material to be transferred or coated coat, or the fabric to be printed or transferred. In addition to various printing methods such as coating coating method, screen printing, letterpress printing, etc., in recent years, such a functional resin and / or a functional colored resin component can be obtained by an inkjet coating method (IJ coating method). Transfer or coating, or printing or transferring has been studied or put into practical use. For this purpose, water-based ink compositions for fabrics used as transfer media or coating-coating media, printing media or transfer media, and aqueous coating-coating agents have been widely studied.

  For example, in [Patent Document 3], a monomer composition containing a specific monomer used in printing ink, inkjet (IJ) recording ink, and the like, an oil-soluble dye, and an organosilicon monomer are polymerized. A colored resin emulsion containing, for example, colored fine particles having an average particle size of 92 nm, which has been emulsion-polymerized in combination with an initiator, a reactive emulsifier (or polymerizable emulsifier) and a non-polymerizable emulsifier has been proposed.

  [Patent Document 4] discloses that, in an aqueous medium, as a water-based printing ink for ink jet recording paper, the volume average particle size containing an oil-soluble dye is 70 nm or less, and the hydrophilic polymer portion is 10 to 40% by mass. In addition, a water-based printing ink for IJ recording paper has been proposed in which colored fine particles having a hydrophobic polymer portion of 60 to 90% by mass with Tg ≦ 0 ° C. and particularly Tg ≦ −15 ° C. are dispersed.

  Furthermore, [Patent Document 5] describes an aqueous emulsion type in which resin particles and pigment particles obtained by copolymerizing monomers having functional groups such as a nitrile group, a carboxyl group, and a vinyl group are dispersed at Tg ≦ 0 ° C. An ink composition for fabrics has been proposed, and it is described that it is a fabric ink composition having a washing resistance by exerting an adhesive force on a fabric composed of natural fibers and synthetic fibers.

JP 2000-110069 A Japanese Patent Laid-Open No. 11-124497 JP 2000-297126 A JP 2004-323723 A JP-A-8-209052

  Under such circumstances, the fabric is impregnated or transferred or coated with a functional resin or various functional agents, and “waterproof, water-repellent, quick-drying, antifouling, antistatic, wrinkle-proofing” In addition to the technical field of imparting functions such as `` prevention, form stability, pollen adhesion, antibacterial deodorization, tobacco deodorization '' to functional fabrics, this functional resin component has a coloring function. The technical field is to transfer or coat coat the fabric as a component, transfer the desired "design and / or characters" to the fabric, and make the fabric with a pattern, a functional resin component or a functional colored resin component. It can also be said to be a surface treatment of a fabric that imparts various functions to the fabric by transferring or coating the fabric.

  From the above viewpoints, the latter treatment technique that transfers and forms a pattern and / or characters on a fabric using a functional colored resin prints a desired pattern and / or characters on the fabric as a surface treatment of the fabric. Or it can be said that it is the surface processing to transfer. Therefore, both of the former processing technology for “transferring or coating” the “functional resin component” on the fabric and the latter processing technology for “printing or transferring” the “functional colored resin component” on the fabric. It is understood that the technical scope is the same as a surface treatment process that imparts a function to the fabric ground.

  In addition, as already mentioned above, surface treatments that impart various functions to fabrics are becoming increasingly sophisticated, multifunctional, or diversified, and their technical issues are also increasingly fine, thin, and high performance. In the direction of In addition, in order to achieve the technical problem, in recent years, “nanotech” technology using a material “nanomaterial” is indispensable. That is, the functional resin component and / or the coloring functional component contained in the medium composition described above has, for example, a resin particle size or a transfer / coating coat film thickness of several hundred nm or less, particularly 10 nm. Target ultrafine particles or ultrathin films of ˜several tens of nm. Therefore, it is necessary to search widely for a functional resin material or a functional colored resin material that is a “nanomaterial” as an appropriate material.

  Therefore, in the above-mentioned [Patent Document 3] or [Patent Document 4], colored resin fine particles having ultrafine particles of about several tens of nanometers of submicron or less and Tg ≦ 0 ° C. have been proposed. [Patent Document 5] discloses an aqueous emulsion ink composition in which resin particles having a functional group such as a nitrile group, a carboxyl group, and a vinyl group and pigment particles are dispersed at Tg ≦ 0 ° C. It is described as a water-based emulsion ink composition having a washing resistance by exerting an adhesive force on a fabric.

  However, various functional resin compositions including colored resin fine particles that have been proposed as conventional techniques exhibit excellent transferability or coating coatability on fabrics, and also have excellent laundry resistance. In fact, it is not always clearly stated or disclosed whether or not the material is capable of imparting sufficient functions to the fabric and its functional effects are sufficient to exhibit durability.

Accordingly, an object of the present invention is to transfer or coat a functional resin composition or a functional colored resin composition to a fabric, for example, different from the prior art (1) or (2) as described below. It is to propose a “nanomaterial” resin component that allows the fabric to exhibit transferability or coating coatability under hot press, and to give the resin component a function with excellent washing resistance. In addition, the resin component that has been transferred or coated has been developed to exhibit functions such as oil repellency having excellent washing resistance and antifouling properties, and the functional effects that have been exhibited are extremely durable and robust. It is to provide an aqueous emulsion type resin composition for a certain fabric.
(1) After impregnating or coating a functional resin component on a woven fabric or non-woven fabric made of various natural fibers and / or synthetic fibers, laminating is performed under a hot press to impart a function to the fabric. Is a functional fabric.
Or
(2) A pattern-attached fabric in which patterns and / or letters are pattern-dyed using an oil-soluble or water-soluble dye in advance, and then the resin component is sprayed, applied, and thermocompression bonded to transfer the function to the fabric. Some are common.

  Another object of the present invention is to provide an aqueous emulsion-type resin composition that exhibits the above-described characteristics and imparts excellent washing resistance to oil repellency and antifouling function to a fabric under hot press. To provide a functional fabric formed by transferring or coating the fabric.

  Further, another object of the present invention is to use an aqueous emulsion resin composition for fabrics that imparts oil repellency having anti-washing properties and antifouling properties to the fabric as described above. It is to provide a water-based ink composition for fabrics that exhibits printability and transferability as transferability under hot press by having both properties.

  Further, another object of the present invention is to use a water-based ink composition exhibiting such features and functions, to various images and / or non-woven fabrics by various printing and transfer methods. Or to provide a printed fabric in which characters are printed or transferred under hot press.

  Therefore, as a result of intensive investigations on the above-described problems, the present inventors have determined that ultrafine polymer particles that are “nanomaterials” having a specific glycidyl group and “nanomaterials” that have a specific carboxyl group are identified. When an aqueous emulsion containing fine polymer particles is applied to a fabric and attention is focused on causing interaction between both functional groups under thermocompression bonding, the functional resin component or the functional colored resin component is effective. It was found that it was transferred to a fabric, and the present invention was completed.

  According to the present invention, the resin component dispersed in the aqueous medium exhibits transferability or coating coatability on the fabric under hot press, and the transfer or coating coat resin component has excellent washing resistance. Provided is a water-based emulsion-type resin composition for fabrics, which imparts oil repellency and antifouling function to the fabric, and the imparted functional effect is extremely durable and fast.

That is, the resin component contained in the water-based emulsion type resin composition for fabric according to the present invention and exhibiting the characteristics and functions described above is copolymerizable having a glycidyl group per 100% by mass of the total polymerizable monomer component. It is a copolymer particle obtained by copolymerizing the monomer component in the range of 10 to 70% by mass. And it contains as nanomaterial resin component (A) (or 1st resin component) of the ultrafine polymer particle whose average particle diameter represented on a volume basis is 5-100 nm.
Further, the copolymerizable monomer component having a carboxyl group is obtained by copolymerization in the range of 0.1 to 20% by mass per 100% by mass of the total polymerizable monomer component, and the average particle size expressed by volume is 5 nm. It is contained as a nanomaterial resin component (B) (or second resin component) of ˜1 μm ultrafine polymer particles.
After the aqueous emulsion type resin composition containing the first resin component and the second resin component is applied to the fabric, the functional groups of the first resin component and the second resin component under hot press are changed. Acting under chemical interrelation, transfer or coat coat to fabric.

  Further, according to the present invention, the coated coated body is composed of any one fiber selected from the group consisting of natural fibers, recycled fibers, semi-synthetic fibers, and synthetic fibers, each of which is a single fiber, and at least two types of these composite fibers. By applying a water-based emulsion-type resin composition for a fabric according to the present invention that exhibits such features and functions to a woven fabric or a non-woven fabric under hot press, the coated coating resin component has excellent washing resistance. Provided is a functional fabric characterized by having an oil repellency and an antifouling function.

  In addition, according to the present invention, an ultrafine polymer that is a first resin component dispersed in an aqueous medium using the aqueous emulsion resin composition for fabric according to the present invention that exhibits the above-described features and functions. By making the nanomaterial resin component (A) of the particles into a colored resin component having coloring properties, it is hot-pressed under the relationship with the contained nanomaterial resin component (B), Demonstrate printability as transferability on a certain fabric. In addition, the printing or transfer coloring resin component comprising the first and second resin components is used for a fabric characterized by exhibiting washing-resistant oil repellency, antifouling properties, and anti-print bleeding properties. A water-based ink composition is provided.

That is, 10 to 70 of the copolymerizable monomer component having a glycidyl group per 100% by mass of the total polymerizable monomer component using the aqueous emulsion resin composition for fabric according to the present invention that exhibits the above-described features and functions. An ultrafine polymer having an average particle diameter of 5 to 100 nm expressed on a volume basis, in which 0.1 to 50% by mass of an oil-soluble dye is encapsulated and colored in copolymer polymer particles obtained by copolymerization in a mass% range. It is contained as the “colored nanomaterial” resin component (A) (or first resin component) of the particles.
Further, the copolymerizable monomer component having a carboxyl group is obtained by copolymerization in the range of 0.1 to 20% by mass per 100% by mass of the total polymerizable monomer component, and the average particle size expressed by volume is 5 nm. It is contained as a “nanomaterial” resin component (B) (or first resin component) of ultrafine polymer particles of ˜1 μm.
As described above, the first colored resin component and the second resin component dispersed in the water-based ink composition exhibit printing or transferability on the fabric under chemical interrelation under hot press.

  Furthermore, according to the present invention, the water-based ink composition for fabrics according to the present invention that exhibits such characteristics and functions is a natural fiber, a recycled fiber, a semi-synthetic fiber, or a synthetic fiber, which is a printed material or a transferred material. In a woven or non-woven fabric made of any one fiber selected from the group consisting of a single fiber and at least two kinds of these composite fibers, under hot press, for example, by various printing methods or transfer methods including an inkjet method. Printed and transferred. In addition, the colored resin component consisting of the first and second resin components thermocompression bonded as the design and / or characters has functions such as oil repellency, antifouling property, and anti-print bleeding property having excellent washing resistance. A printed fabric characterized in that is provided.

  From the above, when the aqueous emulsion resin composition according to the present invention is applied to a fabric, the first resin component of the nanomaterial resin component (A) of the ultrafine polymer particles and the nanomaterial resin component of the ultrafine polymer particles ( The second resin component of B) quickly penetrates into the fabric ground including the fine fiber gaps of the fabric and effectively conforms and adheres to the fabric. Moreover, the first resin component of the nanomaterial resin component (A) having a glycidyl group and the second resin component having a carboxyl group are located very close to each other. Furthermore, the nanomaterial resin component (A) and the nanomaterial resin component (B) are formed so that glycidyl groups and carboxyl groups exist on the surfaces of the ultrafine polymer particles.

  As a result, by applying an aqueous emulsion resin composition to the fabric and thermocompression bonding, a very effective chemistry between the functional groups of the first resin component (A) and the second resin component (B) is achieved. The resin component including the first resin component (A) and the second resin component (B) is transferred or coated on the fabric by expressing a mechanical interaction (or interact).

  Thus, under the hot press (or thermocompression bonding), the interaction as described above is utilized in the resin component that is transferred or coated on the fabric by exhibiting the transfer or coating coat property on the fabric, The resin component that has been transferred or coated exhibits excellent washing resistance.

  In addition, since these transfer properties, coating coat properties, or washing resistance characteristics and functions are exhibited, these resin components are imparted with various functions including coloring, oil repellency, antifouling properties, and the like. be able to. In addition, the functional effects imparted compared to the materials of the prior art are remarkably sustained and robust.

  In addition, the functional resin component contained in such an aqueous emulsion resin composition or a functional coloring resin component thereof is used as a functional colored resin component to transfer or coat the fabric, or to perform printing or transfer. Depending on the processing to be performed, various functional fabrics and various printing fabrics can be processed.

  In particular, in the water-based ink composition for fabrics according to the present invention, the nanomaterial coloring resin component (A) of the ultrafine polymer particles that are printed or transferred to the fabric under hot press and encapsulate the dye, The intervening resin component (B) interacts to effectively prevent bleeding of the ink component from the colored resin component containing the ink component, thereby exhibiting so-called “print-proof bleeding”.

  From the above, regarding the water-based emulsion resin composition that exhibits transferability or coating coatability on the fabric under hot press according to the present invention and the water-based ink composition for fabric that exhibits printability or transferability under hot press, The best mode for implementation will be further described.

As already explained, the first resin component and the second resin component contained in the aqueous emulsion resin composition for fabric according to the present invention that exhibits transferability or coating coatability under hot press on the fabric,
(A) A copolymer monomer component having a glycidyl group is obtained in an amount of 10 to 70% by mass per 100% by mass of the total polymerizable monomer component, and is an acrylic copolymer particle.
(B) A first resin component that is a “nanomaterial” resin component (A) of ultrafine polymer particles having an average particle diameter of 5 to 100 nm expressed on a volume basis of the acrylic copolymer particles.
(C) Further, the copolymerizable monomer component having a carboxyl group is obtained in the range of 0.1 to 20% by mass per 100% by mass of the total polymerizable monomer component, and the average particle size expressed by volume is 5 nm to 1 μm. It is characterized by being a second resin component which is a “nanomaterial” resin component (B) of the ultrafine polymer particles.

In addition, the colored resin component contained in the water-based ink composition for fabric according to the present invention that exhibits printability or transferability under hot press with respect to the fabric,
(D) In addition to the features (i) to (c) described above, as a further feature, the first resin component is preliminarily encapsulated with an oily dye in the range of 0.1 to 50% by weight. Nanomaterial ”is characterized by being a resin component.

From the above, the water-based emulsion-type resin composition for fabric or the water-based ink composition for fabric according to the present invention includes:
(E) Under hot press (or thermocompression bonding) after applying to the fabric, the functional groups of each of the first resin component and the second resin component contained are acting in a chemical relationship. Transfer or coat the fabric. Or it is characterized by printing or transferring.

  As already described above, the acrylic copolymer particles used as the first resin component have a copolymerizable monomer component having a glycidyl group in an amount of 10 to 70% by mass per 100% by mass of the total polymerizable monomer component. Copolymer polymer particles obtained by polymerization. In the present invention, when the amount of the copolymerizable monomer component having a glycidyl group is less than the lower limit value of 10% by mass, the content of the glycidyl group is small, and the transferability or coating coatability under hot press is inferior and significantly reduced On the other hand, when the upper limit of 70% by mass is exceeded, the adhesive component is small, and the fixability before hot pressing is remarkably lowered.

  The average particle diameter of the copolymer polymer particles (A) obtained under such copolymerization is 5 to 100 nm ultrafine particles expressed on a volume basis, and preferably in the range of 10 to 60 nm. It is a certain “nanomaterial” resin component (A). When this average particle diameter is less than the lower limit of 5 nm, it is not preferable because the formation / productivity of the particles is decreased, and the fixability to the fiber is decreased. On the other hand, when the upper limit of 100 nm is exceeded, It is not preferable because the adhesive component is lowered and transferability before hot pressing is significantly reduced.

  Furthermore, the nanomaterial resin component (B) of the acrylic polymer particles used for the second resin component is a copolymerizable acrylic monomer having a carboxyl group per 100% by mass of the total polymerizable monomer component as described above. It is obtained by polymerizing the components in the range of 0.1 to 20% by mass. If the amount of the copolymerizable monomer component having a carboxyl group is less than the lower limit of 0.1% by mass, the reactivity with the glycidyl group is inferior and the fixing property is lowered. On the other hand, the upper limit is 20% by mass. If it exceeds 50%, an unreacted binder component remains, which is not preferable because a sticky feeling is exhibited.

  The average particle diameter of the copolymer polymer particles (B) obtained under such copolymerization is 5 nm to 1 μm ultrafine particles expressed on a volume basis, preferably in the range of 20 to 500 nm. It is a certain “nanomaterial” resin component (B). If the average particle diameter is less than the lower limit of 5 nm, the resin particles flow from the fiber gaps of the fabric and are not preferable because the fixing is significantly reduced. On the other hand, if the upper limit exceeds 1 μm, the resin particles are not present in the fiber gaps. It is not preferable because it is difficult to penetrate.

  Therefore, in the present invention, examples of the monomer having a glycidyl group used for the preparation of the acrylic copolymer particles (A) that are the first resin component having the above-described characteristics include, for example, glycidyl (meth) acrylate and allyl glycidyl ether. Glycidyl group-containing vinyl compounds such as glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid; β-methylglycidyl (meth) acrylate; glycidyl vinyl ether having an epoxy group, glycidyl vinyl ester, 3,4-epoxycyclohexyl vinyl ether, Examples thereof include glycidyl (meth) allyl ether, 3,4-epoxycyclohexyl (meth) allyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like. In particular, in the present invention, when an acrylic acid alkyl ester, which will be described later, is used as a copolymerization component, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meta) is obtained from the copolymerizability with the copolymerization component and the polymerization reaction rate. ) A (meth) acrylic monomer having a glycidyl group such as acrylate is preferred.

  In the present invention, the monomer having a carboxyl group used for preparing the nanomaterial resin component (B) having binder properties as the second resin component having the above-described characteristics includes, for example, acrylic acid, methacrylic acid, Itaconic acid, maleic acid, citraconic acid, fumaric acid, crotonic acid, isocrotonic acid, methylene malonic acid, itaconic acid monoethyl, itaconic acid monobutyl, maleic acid monomethyl, maleic acid monoethyl, maleic acid monobutyl, maleic acid monopropyl, maleic acid monoacid Octyl, carboxyalkyl vinyl ether, carboxyalkyl vinyl ester, carboxyalkyl (meth) acrylate, and derivatives thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydro Water phthalic acid, and the like. Among them, in the present invention, preferably, an acrylic monomer having a carboxyl group such as acrylic acid, methacrylic acid, carboxyalkyl (meth) acrylate, etc. is suitably used because the binder performance (or adhesiveness) can be sufficiently exhibited. Can be used.

  In preparing the first resin component and the second resin component in the present invention, examples of the acrylic monomer having no functional group used as a copolymerizable monomer component include methyl (meth) acrylate, (meth ) Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate; (meth) Aromatic (meth) acrylic acid esters such as phenyl acrylate; (meth) acrylic Methoxyethyl, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, etc .; fats such as cyclohexyl (meth) acrylate Examples thereof include (meth) acrylic acid esters of cyclic alcohols.

  In the present invention, when the ultrafine polymer particles (A) or the ultrafine polymer particles (B) according to the present invention are prepared by the emulsion polymerization method described later, these ultrafine polymer particles are expressed as necessary. The crosslinked structure can be introduced and formed as long as the above-described features and functions are not inhibited and the formation of such ultrafine polymer particles is not inhibited. As the crosslinking agent, a polyfunctional monomer can be suitably used as appropriate. As the polyfunctional monomer, for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethanetri Examples include acrylate, 1,1,1-trishydroxymethylpropane triacrylate, and the like.

  Further, in the present invention, it is a resin component that exerts transfer or coating coat properties as long as the characteristics and functions of the aqueous emulsion-type resin composition for fabric or the aqueous ink composition for fabric according to the present invention are not impaired. The ultrafine polymer particles (A) and / or the ultrafine polymer particles (B) can usually contain a fluorine compound that exhibits functions such as water repellency. In the present invention, examples of the fluorine-substituted (meth) acrylic monomer include trifluoromethyl methyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, and (meth) acrylic acid-2-par. Fluoromethylethyl, (meth) acrylic acid-2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid-2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meta ) Fluorine-substituted (meth) acrylic acid-based monomers such as dipa-fluoromethyl acrylate.

  Such polyfunctional monomers and fluorine-substituted (meth) acrylic monomers are used in combination with the ultrafine polymer particles according to the present invention as long as the properties of the ultrafine acrylic polymer particles (A) and (B) are not impaired. These monomers can be prepared and used in the range of 0.1 to 10% by mass.

  The nanomaterial coloring resin component dispersed in the water-based ink composition for fabric according to the present invention includes an oil-soluble dye encapsulated in the ultrafine polymer particles contained in the water-based emulsion resin composition, as already described. It contains colored ultrafine polymer particles (A). In the present invention, as long as the oil-soluble dye to be included and colored in the ultrafine polymer particles is dissolved or uniformly dispersed in the above acrylic monomer, it is preferably an oil-soluble dye that is less soluble in water than these monomers. For example, it is appropriately selected without particular limitation.

  As the oil-soluble dye, for example, black Olesolol Fast Black, BONJET BLACK CW-1, Solvent Black 27Cr (trivalent) containing 5%, Pigment Black 7 / water, red VALIFAST RED 3306, Olesolol Fast RED BL, Solvent RED8Cr (3 5.8% Contained, Blue Kayaset Blue, Solvent Blue 35, Yellow ALIFAST YELLOW 4120, Oil Yellow 129, Solvent Yellow 16, Solvent Yellow 33, Disperse Yellow 54, Lemon Piast Yellow 8005, Green Oil Green 502, Opias Green502, Magenta VALIFAST PINK2310N, Plast RED D-54, Plast RED 8355, Plast RED 8360, Plast Vioiet 8850, Disperse Violet 28, Solvent RED149, Solvent RED49, Solvent RED 52, Cyan VALIFAST BLUE2610, VALIFAST BLUE2610, VALIFAST BLUE26 Plast BLUE 8580, Plast BLUE 8540, Oil BLUE 5511, Orange Oil 01, VALIFAST ORANGE 3210, Solvent Orange 70, Kayaset Orange G, can be mentioned VALIFAST BROWN 2402, Solvent Yellow116, Kayaset Flavine FG like brown.

Moreover, for example, solvent blue, solvent red, solvent orange, solvent green, rumogen F orange and the like can be mentioned. In addition, for example, dyes commonly used in writing recording liquids such as clarine, perylene, dicyanopinyl, azo, quinophthalone, aminopyrazole, methine, dicyanoimidazole, indoaniline, phthalocyanine, A leuco dye used as a heat-sensitive recording paper or a temperature-sensitive color material, and, for example, rhodamine B stearate (red 215), tetrachlorotetrabromofluoresene (red 218), tetrabromofluorescene (red 223) No.), Sudan III (red No. 225), dibromofluorescein (orange No. 201), diiodo fluorescein (orange No. 206), fluorescein (yellow No. 201), quinoline yellow SS (yellow No. 204), quinizarin green SS ( Green 202), azurin purple SS (purple 201), medicine Cosmetics such as Scarlet (Red 501), Oil Red XO (Red 505), Orange SS (Orange 403), Yellow AB (Yellow 404), Yellow OB (Yellow 405), Sudan Blue B (Blue 403) The tar-type dye currently used for can also be mentioned.
In the present invention, these dyes are used alone or in admixture of two or more, and if necessary, various direct dyes, acid dyes, basic dyes, azoic dyes, reactive dyes, fluorescent dyes and A fluorescent whitening agent can be appropriately selected and used according to the desired color tone.

  In the present invention, these dyes are used alone or in admixture of two or more, and if necessary, various direct dyes, acid dyes, basic dyes, azoic dyes, reactive dyes, fluorescent dyes and A fluorescent whitening agent or the like can be appropriately selected and used according to the desired color tone. In the present invention, expressed in terms of mass, per 100% by mass of the nanomaterial resin component of the ultrafine polymer particles already described above, in the range of 0.1 to 50% by mass, preferably in the range of 1 to 20% by mass. The inclusion color can be appropriately and suitably applied.

  In the present invention, a water-based emulsion resin composition or water-based ink composition according to the present invention is transferred or coated on a fabric, or is transferred or coated on a fabric. Examples of fabrics to be transferred include natural fibers such as cotton / cotton, hemp, wool, silk, and cashmere; regenerated fibers such as rayon, cupra, and tencel; semisynthetic fibers such as acetate and triacetate; nylon, polyester, and acrylic And a woven fabric or a non-woven fabric made of any one fiber selected from the group consisting of individual fibers of synthetic fibers such as polyolefin, polyvinyl chloride, vinylon, vinylidene, polyurethane, polyamide, and at least two types of these composite fibers. it can.

  In addition, in order to transfer, coat, or print or transfer the aqueous emulsion resin composition or aqueous ink composition according to the present invention to the above-described fabric, a blade coater and an air knife, which are conventionally known methods and apparatuses, are used. Examples thereof include a coat, a roll coater, a bar coater, a gravure coater, a rod blade coater, a die coater, ink jet coating, letterpress printing, screen printing, and ink jet printing.

<Other additives and functional agents>
In addition, unless the formation of the ultrafine particle polymer particles or colored ultrafine particle polymer particles according to the present invention is inhibited, or the transferability or coating coatability of the fabric exhibited by the nanomaterial resin component, or the printability is not inhibited. In addition, if necessary, other known additives (compounding agents) can be blended to exhibit other functions reflected by these additives. In the present invention, examples of such additives include heat stabilizers, dispersants, preservatives, water repellents, viscosity modifiers, anti-sagging agents, surface tension regulators, pH regulators, antifoaming agents, and chelates. Agents, antioxidants, antistatic agents, near infrared absorbers, ultraviolet absorbers, antibacterial / antifungal agents, fragrances, fluorescent agents, organic EL luminescent agents, various medicinal components, and the like can be added as appropriate.

<Preparation of water-based emulsion resin composition for fabric according to the present invention>
Therefore, it has such characteristics, exhibits transfer or coating coat properties on the fabric under thermal transfer, has excellent washing resistance, and has oil repellency, antifouling properties, and printing colorability on the fabric. The preparation method of the aqueous emulsion resin composition for fabrics according to the present invention to be applied will be described below.

As already explained, in the aqueous emulsion type resin composition for fabrics according to the present invention, the first resin component of ultrafine polymer particles having an average particle diameter of 5 to 100 nm prepared by using a usual emulsion polymerization method is used. An aqueous emulsion resin composition containing [nanomaterial resin component (A)] and [nanomaterial resin component (B)] as the second resin component of ultrafine polymer particles having an average particle size of 5 nm to 1 μm. is there.
According to the present invention,
(1) [Nanomaterial resin component (A)] of the first resin component is, for example, 10 to 16 parts by mass of ammonium dodecylbenzenesulfonate as an emulsifier in an aqueous phase of 800 to 950 parts by mass, for example, water-soluble. 10-12 parts by mass of methanol, which is a volatile organic solvent, is heated to 75-90 ° C. with stirring, and then a predetermined amount of ammonium persulfate is added.
Next, a predetermined amount of a predetermined polymerizable acrylic monomer having no functional group and a predetermined polymerizable acrylic monomer having a glycidyl group (or a glycidyl-containing monomer) are heated at 70 to 80 ° C. with stirring. With a predetermined amount of the total polymerizable monomer component (the glycidyl group monomer component is 10 to 70% by mass) and an additional predetermined amount of emulsifier, 1.5 to 3 hours are required for emulsion polymerization and Aged.
As a result, an aqueous emulsion reaction product having a solid content concentration of 10 to 16% as ultrafine polymer particles is prepared at a polymerization rate of approximately 100%. Moreover, the ultrafine polymer particle by this invention prepared in this way is a nanomaterial resin component (A) in which the average particle diameter represented on a volume basis exists in the range of 5-100 nm.
Then
(2) [Nanomaterial resin component (B)] of the second resin component is, for example, 10 to 16 parts by mass of ammonium dodecylbenzenesulfonate in an aqueous phase of 800 to 950 parts by mass; After adding 12 parts by mass and raising the temperature to 75 to 90 ° C. with stirring, a predetermined amount of ammonium persulfate is added.
Next, a predetermined amount of a predetermined polymerizable acrylic monomer having no functional group and a predetermined polymerizable acrylic monomer having a carboxyl group (or a carboxyl group-containing monomer) are heated under stirring at 70 to 85 ° C. It takes 1.5 to 2.5 hours together with a predetermined amount of the total polymerizable monomer component (carboxyl-containing monomer component is 0.1 to 20% by mass) and an additional predetermined amount of emulsifier. Under emulsion polymerization. Subsequently, after hold | maintaining for 30 to 40 minutes at 70-80 degreeC, 80-85 degreeC heating and aging are hold | maintained for 1 to 2 hours. As a result, an aqueous emulsion reaction product is prepared in which the resin component of ultrafine particles having an average particle diameter of 5 nm to 1 μm is dispersed at a solid content concentration of 10 to 14%.

  From the above, the water-based emulsion type resin composition for fabric according to the present invention includes the first resin component “nanomaterial resin component (A)” and the second resin component “nanomaterial resin component (B)” prepared as described above. Preferably, it is an aqueous emulsion type that is appropriately mixed at a ratio of “nanomaterial resin component (A)” / “nanomaterial resin component (B)” = 97/3 to 60/40 in mass fraction. The resin composition is suitably used as appropriate.

  In the present invention, in the mixing ratio of the “nanomaterial resin component (A)” and “nanomaterial resin component (B)”, as already explained, under the hot press after being applied to the fabric, When component (A) "exceeds 97% by mass, the amount of" nanomaterial resin component (B) "that is a binder component is too small, which is not preferable because transferability or coating coatability is lowered. On the other hand, when the “nanomaterial resin component (A)” is less than 60% by mass, the “nanomaterial resin component (B)” component is too much to reduce transferability or coating coatability, and washing resistance In the present invention, it is more preferable that an aqueous emulsion resin composition having a mixing ratio of 90/10 to 70/30 is appropriately used. Can be prepared.

  The aqueous emulsion resin composition according to the present invention containing the “nanomaterial resin component (A)” and the “nanomaterial resin component (B)” prepared by the emulsion polymerization method as described above, Under the thermocompression bonding (or hot press) after being applied to the fabric, good transferability or coatability is exhibited. Further, various functions can be imparted to the fabric by the transfer or coating coat resin component.

  Therefore, in the present invention, the emulsifier used for the emulsion polymerization described above is conventionally an anionic surfactant, a cationic surfactant, or a nonionic surfactant as necessary, which is usually used as an emulsifier. They can be selected as appropriate and used alone or in combination. For example, examples of the anionic surfactant include dodecyl benzene sulfonate, undecyl benzene sulfonate, tridecyl benzene sulfonate, and nonyl benzene sulfonate. Examples of the cationic surfactant include cetyltrimethylammonium promide, hexadecylpyridinium chloride. , Hexadecyltrimethylammonium chloride and the like, and nonionic surfactants include lipidinium and the like. Furthermore, a reactive emulsifier having a polymerizable group such as an acryloyl group or a methacryloyl group can be used. These emulsifiers are used without particular limitation. Moreover, in this invention, these emulsifiers are 1-50 mass parts with respect to 100 mass parts of polymerizable monomers, such as an acryl-type monomer mentioned above, Preferably it is made to add suitably in the range of 3-20 mass parts. it can. If the amount of the emulsifier is small, the particle diameter of the resin fine particles obtained tends to be large, whereas if it is large, the particle diameter tends to be small. Also in the present invention, the average particle diameter of the resin fine particles can be appropriately adjusted within a range of 5 to 100 nm on a volume basis under a predetermined stirring speed.

  Further, the aqueous medium contained in the aqueous emulsion resin composition according to the present invention is any one appropriately selected from methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran and the like in the aqueous phase of the main aqueous component. The water-soluble organic solvent can be contained. In addition, these water-soluble organic solvents are so-called dye hydrophilization aids in forming dye-colored resin particles by effectively encapsulating and fixing oil-soluble dyes that are encapsulated and colored under emulsion polymerization as described later. It can be said that it acts as.

<Preparation of water-based ink composition for fabric according to the present invention>
According to the present invention, the water-based ink composition for a fabric according to the present invention that exhibits printability or transferability as a transfer property under thermocompression bonding after being applied to the fabric is a water-based fabric for fabric according to the present invention already described above. The ultrafine polymer particles of the “nanomaterial resin component (A)” contained in the emulsion type resin composition were changed to the colored ultrafine polymer particles of the “colored nanomaterial resin component (A)” encapsulating the oil-soluble dye. Is. From the above, printability or transferability as transferability is exhibited under thermocompression bonding, and the printing or transfer coloring resin component has excellent water repellency, antifouling function, and printing resistance. A method for preparing a water-based ink composition according to the present invention that exhibits bleeding properties and the like will be described below.

According to the present invention,
(1) “Colored nanomaterial resin component (A)” of the first resin component is, for example, 10 to 16 parts by mass of ammonium dodecylbenzenesulfonate in an aqueous phase of 800 to 950 parts by mass, for example, methanol 10 -12 mass parts is added, and after heating up to 75-90 degreeC under stirring, a predetermined amount of ammonium persulfate is added.
Next, a predetermined amount of a predetermined polymerizable acrylic monomer having no functional group and a predetermined polymerizable acrylic monomer having a glycidyl group (or a glycidyl-containing monomer) are heated at 70 to 80 ° C. with stirring. A predetermined amount of the total polymerizable monomer component (the glycidyl group monomer component is 10 to 70% by mass), an additional predetermined amount of emulsifier, and 0.1 to 100% by mass of the resulting copolymer particles. After a predetermined emulsion-polymerization with a predetermined oil-soluble dye to be encapsulated and colored in the range of 50% by mass over 1.5-3 hours, the mixture is held at 70-80 ° C. for 30 minutes and then heated to 85 ° C. For 1 to 2 hours to prepare an aqueous emulsion reaction product having a solid content of 10 to 15% as colored ultrafine polymer particles. Moreover, the colored ultrafine polymer particles according to the present invention prepared in this way are nanomaterial resin components (A) having an average particle diameter in a range of 5 to 100 nm on a volume basis.
Then
(2) The second resin component [nanomaterial resin component (B)] is, for example, 10 to 16 parts by mass of ammonium dodecylbenzenesulfonate and, for example, methanol 10 to 12 in an aqueous phase of 800 to 950 parts by mass. After adding a mass part and heating up to 75-90 degreeC under stirring, a predetermined amount of ammonium persulfate is added.
Next, a predetermined amount of a predetermined polymerizable acrylic monomer having no functional group and a predetermined polymerizable acrylic monomer having a carboxyl group (or a carboxyl group-containing monomer) are heated under stirring at 70 to 85 ° C. Together with a predetermined amount in the range of 0.1 to 20% by weight of this carboxyl-containing monomer component and an additional predetermined amount of emulsifier, with respect to 100% by weight of the total polymerizable monomer component with a predetermined amount, 1.5-2. It takes 5 hours to perform emulsion polymerization by pouring.
Subsequently, after hold | maintaining for 30 to 40 minutes at 70-80 degreeC, 80-85 degreeC heating and aging are hold | maintained for 1 to 2 hours. As a result, an aqueous emulsion reaction product is prepared in which ultrafine resin components having an average particle diameter of 5 nm to 1 μm are dispersed at a solid content concentration of 10 to 14%.

  From the above, the water-based ink composition for fabric according to the present invention includes the first resin component “colored nanomaterial resin component (A)” and the second resin component “nanomaterial resin component (B)” prepared as described above. Preferably, it is expressed as a mass fraction, “colored nanomaterial resin component (A)” / “nanomaterial resin component (B)” = 97/3 to 60/40, which is appropriately mixed in an aqueous emulsion type The water-based ink composition is suitably used as appropriate.

In the present invention, as described above, in the mixing ratio of the “colored nanomaterial resin component (A)” and the “nanomaterial resin component (B)”, the “colored nanomaterial resin component (A)” When the “material resin component (A)” exceeds 97% by mass, the “nanomaterial resin component (B)” that is a binder component is too small, which is not preferable because printability or transferability is lowered. On the other hand, when the “colored nanomaterial resin component (A)” is less than 60% by mass, the “nanomaterial resin component (B)” component is too much, which is not preferable because the printing color density is lowered. Can be suitably prepared in an aqueous emulsion resin composition in which the mixing ratio of the two is in the range of 90/10 to 70/30.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1
An aqueous emulsion-type resin composition for fabric containing “nanomaterial resin component (A)” and “nanomaterial resin component (B)” is prepared, applied to a cotton fabric, and oil-repellent and Examples of imparting antifouling properties to fabrics are described below.
<Water-based emulsion resin composition for fabric according to the present invention>
(1) Preparation of “Nanomaterial Resin Component (A)” In a 4-liter flask with a capacity of 1 liter equipped with a thermometer and a nitrogen introduction tube, 900 parts by mass of ion-exchanged water and ammonium dodecylbenzenesulfonate 14 as an emulsifier After adding a mass part and 14 mass parts of methanol, and heating up to 85 degreeC, 0.6 mass part of ammonium persulfate was added. Next, while maintaining the temperature at 76-78 ° C,
-87 parts by mass of methyl methacrylate (MMA),
-13 parts by weight of glycidyl methacrylate (GMA),
Polymerization was carried out by pouring 1 part by mass of ammonium salt of dodecylbenzenesulfonic acid as an emulsifier over 2 hours. Furthermore, after maintaining at 76-78 ° C. for 30 minutes, the temperature was raised to 85 ° C. and then maintained for 1.5 hours.
As a result, the polymerization rate was about 100%, the solid content in the obtained aqueous emulsion reaction product was 12%, and the resin component of the solid content was “nanomaterial of ultrafine polymer particles having an average particle size of 30 nm. Resin component (A) ”emulsion (a) was obtained.

(2) Preparation of “Nanomaterial Resin Component (B)” A 4-liter flask with a capacity of 1 liter, equipped with a thermometer and a nitrogen inlet tube, 900 parts by mass of ion-exchanged water and an emulsifier, ammonium dodecylbenzenesulfonate 14 Part by mass and 14 parts by mass of methanol were added, the temperature was raised to 85 ° C., and 0.6 part by mass of ammonium persulfate was added.
Next, while maintaining the temperature at 76-78 ° C,
-75 parts by weight of butyl acrylate (BA),
-20 parts by mass of 2-ethylhexyl acrylate (2-EHA);
-5 parts by weight of methacrylic acid (MAA);
1 part by mass of emulsifier dodecylbenzenesulfonic acid ammonium salt was dropped over 2 hours to perform drop polymerization. Furthermore, after hold | maintaining at 76-78 degreeC for 30 minutes, it heated up to 85 degreeC and hold | maintained for 1.5 hours. As a result, an emulsion (b) having a polymerization rate of about 100%, a solid content of 12%, and an average particle size of 20 nm was obtained.
The emulsion (c) was prepared by adjusting the solid content ratio of the emulsion (a) and the emulsion (b) to 7: 3.

<Preparation of functional fabric>
Next, the emulsion (c) was uniformly applied to a 10 cm square cotton fabric with a sprayer, dried at room temperature, and then hot-pressed with an iron. Commercially available oil-based ink droplets were spotted at four locations on the fabric where the washing cycle of “hand washing with laundry detergent” and “room temperature drying” was performed 10 times. Next, after leaving it for 3 hours, the fabric which was lightly hand-washed in a thin detergent solution did not show any traces of oil or contamination due to ink droplets.
From the above, the water-based emulsion type resin composition for fabrics according to the present invention was coated with a fabric and hot-pressed, whereby it was possible to impart oil-repellent and antifouling dyes having wash resistance to the fabric.

(Example 2)
After preparing a water-based ink composition for a fabric containing “colored nanomaterial resin component (A)” and “nanomaterial resin component (B)”, and printing a bold character on a polyester fabric by handwriting And hot pressed with an iron.
Next, the printability or transferability of the printed characters and the washing resistance were evaluated by the color change evaluation method of the printed characters on which the fabric was subjected to 10 washing cycles of “hand washing with laundry detergent” and “room temperature drying”. The results are shown in Table 1.
In addition, the letters on the fabric before washing were overwritten with small letters with commercially available blue oil-based ink, then left at room temperature for 3 hours, and then the letters on the fabric lightly hand-washed in a thin detergent solution were completely blue. No traces of oily or blue contamination were seen. From the above, it is understood that oil-repellent and antifouling properties are imparted to printed characters on the fabric.

<Water-based ink composition for fabric according to the present invention>
(1) Preparation of “Colored Nanomaterial Resin Component (A)” In a 1-liter four-necked flask equipped with a thermometer and a nitrogen introduction tube, 900 parts by mass of ion-exchanged water and an emulsifier, ammonium dodecylbenzenesulfonate 14 parts by mass and 11.2 parts by mass of methanol were added and the temperature was raised to 85 ° C., and then 0.5 parts by mass of ammonium persulfate was added. Next, while maintaining the temperature at 76-78 ° C,
-90 parts by mass of methyl methacrylate (MMA),
-10 parts by weight of glycidyl methacrylate (GMA),
-5 parts by mass of the oil-soluble dye "Solvent RED 49"
Polymerization was carried out by pouring 1 part by mass of ammonium salt of dodecylbenzenesulfonic acid as an emulsifier over 2 hours. Furthermore, after maintaining at 76-78 ° C. for 30 minutes, the temperature was raised to 85 ° C. and then maintained for 1.5 hours.
As a result, the polymerization rate was about 100%, the solid content in the obtained aqueous emulsion reaction product was 12%, and the resin component of the solid content was “colored nano-particles of ultrafine polymer particles having an average particle diameter of 20 nm. Emulsion (d) of “material resin component (A)”.

(2) Preparation of “Nanomaterial Resin Component (B)” A 4-liter flask with a capacity of 1 liter equipped with a thermometer and a nitrogen introduction tube was charged with 900 parts by mass of ion-exchanged water and an emulsifier ammonium dodecylbenzenesulfonate 14 Part by mass and 11.2 parts by mass of methanol were added, the temperature was raised to 85 ° C., and 0.5 parts by mass of ammonium persulfate was added.
Next, while maintaining the temperature at 76 to 78 ° C, 76 parts by mass of butyl acrylate (BA),
-20 parts by mass of 2-ethylhexyl acrylate (2-EHA);
-4 parts by weight of methacrylic acid (MAA);
1 part by mass of emulsifier dodecylbenzenesulfonic acid ammonium salt was dropped over 2 hours to perform drop polymerization. Furthermore, after hold | maintaining at 76-78 degreeC for 30 minutes, it heated up to 85 degreeC and hold | maintained for 1.5 hours. As a result, an emulsion (e) having a polymerization rate of about 100%, a solid content of 12%, and an average particle size of 26 nm was obtained.
Thus, emulsion (i) was prepared as Example 2 in which the solid content ratio of emulsion (d) and emulsion (e) was adjusted to 8: 2.

(Examples 3 and 4)
In Example 3, the emulsion (j) was prepared by adjusting the solid content ratio of the emulsion (d) and the emulsion (e) to 6: 4. In Example 4, the emulsion (k) was prepared by adjusting the solid content ratio of the emulsion (d) and the emulsion (e) to 8.5: 1.5.

(Comparative Example 1)
In preparing the “colored nanomaterial resin component (A)” in Example 2, 10 parts by mass of glycidyl methacrylate (GMA) was changed to 10 parts by mass of 2-methacryloyloxyethylphthalic acid. Similarly, “colored nanomaterial resin component (A)” was prepared. As a result, the polymerization rate was about 100%, the solid content in the obtained aqueous emulsion reaction product was 12%, and the resin component of the solid content was “colored nano-particles of ultrafine polymer particles having an average particle size of 26 nm. It was set as the emulsion (f) which is material resin component (A) -1 ".

(Comparative Example 2)
In preparing “colored nanomaterial resin component (A)” in Example 2, 10 parts by mass of glycidyl methacrylate (GMA) was changed to 10 parts by mass of diethylaminoethyl methacrylate, and the same as in Example 2 was performed. Colored nanomaterial resin component (A) "was prepared. As a result, the polymerization rate was about 100%, the solid content in the obtained aqueous emulsion reaction product was 12%, and the resin component of the solid content was “colored nano-particles of ultrafine polymer particles having an average particle size of 24 nm. It was set as the emulsion (g) which is material resin component (A) -2 ".

(Comparative Example 3)
When preparing the “colored nanomaterial resin component (A)” in Example 2, the same procedure as in Example 2 was performed except that 10 parts by mass of glycidyl methacrylate (GMA) was changed to 10 parts by mass of 2-hydroxyethyl methacrylate. Thus, “colored nanomaterial resin component (A)” was prepared. As a result, the polymerization rate was about 100%, the solid content in the obtained aqueous emulsion reaction product was 12%, and the resin component of the solid content was “colored nano-particles of ultrafine polymer particles having an average particle diameter of 25 nm. It was set as the emulsion (h) which is material resin component (A) -3 ".

<Washing resistance evaluation method by color tone change evaluation method>
The solid contents of emulsions (d) and (f) to (k) were adjusted to 6%, respectively, and dyed on polyester cloth and dried.
・ As it is dried at room temperature as a blank,
-Hand-washed with laundry detergent, hot-pressed with iron, then hand-washed with laundry detergent,
-"Hand washing with laundry detergent" ⇔ "room temperature drying" 10 cycles of washing cycle,
The color change of the color is measured with a measuring instrument (Color Ace MODEL TC-PIII (Tokyo Denshoku Co., Ltd.)) and the value of L * a * b * color system (L * value, a * value, b * value) The “printability or transferability” and its “washing resistance” were evaluated based on the color difference ΔE ^* = (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2 from the blank.
The L * value represents lightness (black, white), and the increasing direction of the numerical value is the black direction. The a * and b * values represent the hue and saturation, the a * value is a red and green index, the increasing method indicates the red direction, and the b * value is yellow and blue. It is an index and the increasing direction of the numerical value is yellow.

表１に示す結果から、本発明による布地用水性インキ組成物のアイロン加熱後のΔＥ値から、布地に対する転着性として印刷性又は転写性が発揮されている証である。また、その洗濯性サイクル試験後のΔＥ値が、アイロン加熱後のΔＥ値に比べて、殆ど差がないことから、布地に印字させたインキ文字は、優れた耐洗濯性を有していることを示している。

From the results shown in Table 1, it is proof that printability or transferability is exhibited as transferability to the fabric from the ΔE value of the aqueous ink composition for fabric according to the present invention after iron heating. In addition, since the ΔE value after the washability cycle test is almost the same as the ΔE value after ironing, the ink letters printed on the fabric have excellent washing resistance. Is shown.

From the above, the aqueous emulsion-type resin composition for fabrics or the aqueous ink composition for fabrics according to the present invention includes the “nanomaterial resin component (A)” of ultrafine polymer particles and the “colored nanomaterial of colored ultrafine polymer particles”. It is a one-pack type that contains the “Nanomaterial resin component (B)” of ultrafine polymer particles that exhibit adhesiveness to the “resin component (A)”, and is an aqueous emulsion that is extremely excellent in handling and handling properties. Various functional fabrics and various designs of woven or non-woven fabrics made of various natural fibers and / or synthetic fibers, simply by transferring or coating to the fabric, printing or transferring, and hot pressing. And a printed fabric on which characters were printed.

Claims (5)

A water-based emulsion type for fabrics that exhibits transferability or coating coat properties under hot press and imparts functions such as oil repellency and antifouling properties with excellent washing resistance to the transfer or coating coat resin component. A resin composition comprising:
Average particle diameter expressed in terms of volume, which is a copolymer particle obtained in a range of 10 to 70% by mass of a copolymerizable monomer component having a glycidyl group per 100% by mass of the total polymerizable monomer component in an aqueous medium. Nanomaterial resin component (A) of ultrafine polymer particles of 5 to 100 nm,
Average particle expressed on a volume basis, which is a copolymer particle obtained by copolymerization of a copolymerizable monomer component having a carboxyl group in a range of 0.1 to 20% by mass per 100% by mass of all polymerizable monomer components. Nanomaterial resin component (B) of ultrafine polymer particles having a diameter of 5 nm to 1 μm,
A water-based emulsion-type resin composition for fabrics, wherein the resin component is transferred or coated on the fabric under hot press as a resin component.   It is contained by the compounding ratio of the said nanomaterial resin component (A) / the said nanomaterial resin component (B) = 97 / 3-60 / 40 expressed with a mass fraction, The Claim 1 characterized by the above-mentioned. An aqueous emulsion resin composition for fabrics.   The water-based emulsion type resin composition for fabric according to claim 1 or 2, wherein each of natural fiber, regenerated fiber, semi-synthetic fiber and synthetic fiber, which is a coated body, is used alone and a group of at least two kinds of these composite fibers. A functional fabric characterized by being provided with an oil repellency and antifouling function having excellent washing resistance by coating a woven or non-woven fabric made of any one of the fibers under hot press under a hot press . Aqueous for fabrics using a water-based emulsion resin composition that imparts functions such as oil repellency and antifouling properties that exhibit transferability or coating coatability to the fabric under hot press, and has wash resistance An ink composition comprising:
Copolymer particles obtained in a range of 10 to 70% by mass of a copolymerizable monomer component having a glycidyl group per 100% by mass of the total polymerizable monomer component in an aqueous medium, and 0.1 to 50 mass of an oil-soluble dye Coloring nanomaterial resin component (A) of ultrafine polymer particles having an average particle diameter of 5 to 100 nm expressed on a volume basis to color the inclusion%,
The copolymer particles obtained in the range of 0.1 to 20% by mass of the copolymerizable monomer component having a carboxyl group per 100% by mass of all the polymerizable monomer components, and the ultrafine particles having an average particle diameter expressed by volume of 5 nm to 1 μm. Containing a nanomaterial resin component (B) of polymer particles,
The printing or transfer resin component comprising the above (A) and (B), which exhibits printability or transferability as transferability under hot press on a fabric to be transferred, has an oil repellency having washing resistance And a water-based ink composition for fabrics, which imparts antifouling and anti-print bleeding functions. Using the water-based ink composition for fabric according to claim 4, each of natural fiber, regenerated fiber, semi-synthetic fiber, and synthetic fiber, which is a printing medium or a transfer medium, is used alone or at least two of these under hot press. A printed fabric, wherein a desired pattern and / or character is printed or transferred to a woven or non-woven fabric comprising any fiber selected from the group of composite fibers.