Printing method

Abstract

To provide a printed fabric that can improve heat resistance of an image printed on a fabric and can also suppress a change in the texture of the fabric before and after printing, and provide a printing method.SOLUTION: A printed fabric is a fabric dyed with a dispersible dye. The fabric is given a dyeable resin. The resin is dyed with the dispersible dye. The dispersible dye is crystallized.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a printed fabric and a printing method, and more particularly to a printed fabric and a printing method that achieve both improved heat resistance of an image printed on a fabric and suppressed change in the texture of the fabric before and after printing. [Background technology]

[0002] Conventionally, textile printing methods have been known in which a desired image is printed on fabric using an ink containing a disperse dye. Examples of such methods include a method in which ink containing a disperse dye is directly applied to fabric to perform printing (direct textile printing), and a method in which ink containing a disperse dye is applied to a transfer medium and then transferred from the transfer medium to perform printing (transfer textile printing = sublimation transfer). The application of the ink is usually performed using an inkjet system, which allows dyeing in a short time and provides high production efficiency.

[0003] Disperse dyes are generally hydrophobic, and therefore easily fixed to fabrics made of hydrophobic polyester fibers, facilitating appropriate printing. However, for fabrics made of other materials, such as fabrics containing hydrophilic fibers such as natural fibers, the disperse dyes do not penetrate and fix sufficiently, making it difficult to properly print, due to the large difference in polarity between the disperse dyes and the fabric. Therefore, studies have been conducted to improve the fixability of inks containing disperse dyes for fabrics other than polyester fiber fabrics (particularly fabrics containing hydrophilic fibers such as natural fibers).

[0004] Methods for improving ink fixability include pretreating fabrics such as natural fibers and applying dyeable resins to the fabric, providing a resin coating layer on the surface of printed fabric (see, for example, Patent Documents 1 to 4), and combinations of these methods (see, for example, Patent Documents 5 and 6).

[0005] However, the printed fabrics obtained by these methods have problems with the heat resistance of the images printed on the fabric, with dye migration during ironing being a particularly serious problem. Another problem is that the texture of the resulting printed fabric is different from the texture of the fabric before printing. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 7-70955 [Patent Document 2] Japanese Patent Application Publication No. 7-316982 [Patent Document 3] Japanese Patent Application Publication No. 7-173767 [Patent Document 4] Japanese Patent Application Publication No. 7-70921 [Patent Document 5] Japanese Patent Application Publication No. 7-216763 [Patent Document 6] Japanese Patent Application Publication No. 7-3668 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in consideration of the above problems and circumstances, and an object of the present invention is to provide a printed fabric and a printing method that improve the heat resistance of an image printed on a fabric while suppressing changes in the texture of the fabric before and after printing. [Means for solving the problem]

[0008] In the course of investigating the causes of the above problems in order to solve the above problems, the present inventors discovered that in a printed fabric in which a dyeable resin applied to a fabric is dyed with a disperse dye, by crystallizing the disperse dye, the heat resistance of the image printed on the fabric is improved and a printed fabric can be obtained in which the texture of the fabric before printing is maintained, thereby arriving at the present invention. That is, the above-mentioned problems of the present invention are solved by the following means.

[0013] 1 . A printed fabric dyed with a disperse dye, wherein a dyeable resin is applied to the fabric, the resin is dyed with the disperse dye, and the disperse dye is crystallized. Printed fabric 、 A method for printing a fabric to obtain a textile, comprising the steps of: applying the resin to the fabric; a dyeing step of dyeing the resin applied to the fabric with the disperse dye; and A step of causing crystal growth of the disperse dye after the dyeing step. have 、 the crystal growth step includes a step of washing the fabric after the dyeing step with a washing liquid, The washing is carried out by immersing the fabric after the dyeing step in water, The immersion time is within a range of 30 to 120 seconds, The immersion temperature during the immersion is 15 to 25°C, The printed fabric after the crystal growth step is not subjected to heat treatment exceeding 110°C. A textile printing method characterized by the above.

[0014] 2 The dyeing is carried out by a sublimation transfer method. 1 Item 1. A textile printing method according to item 1. [Effects of the Invention]

[0019] The above-mentioned means of the present invention can provide a printed fabric and a printing method that improve the heat resistance of an image printed on a fabric while suppressing changes in the texture of the fabric before and after printing. The mechanism by which the effects of the present invention are manifested or the mechanism of action is not clear, but is speculated as follows.

[0020] When dyeing a fabric provided with a dyeable resin with a disperse dye, the disperse dye, particularly the sublimation dye, is expected to diffuse into the resin in a molecular state. In the printed fabric of the present invention, the disperse dye is intentionally crystallized by crystal growth after dyeing to give a stable crystalline state.

[0021] In order for the crystallized disperse dye in the printed fabric to migrate to other components, it is necessary to return the disperse dye to a molecular state again, which is thought to require a considerable amount of heat energy.For this reason, it is thought that in the printed fabric of the present invention, the amount of disperse dye that migrates to other components when heat energy is applied is reduced compared to conventional printed fabrics in which the disperse dye is not crystallized.

[0022] Furthermore, in the printed fabric of the present invention, the heat resistance is improved by the crystallization of the disperse dye as described above, and no additional excessive protective mechanism such as a resin coating layer is involved, so the texture before printing is hardly impaired. DETAILED DESCRIPTION OF THE INVENTION

[0023] The printed fabric of the present invention is a printed fabric dyed with a disperse dye, characterized in that a dyeable resin is applied to the fabric, the resin is dyed with the disperse dye, and the disperse dye is crystallized. This feature is a technical feature common to or corresponding to each of the following embodiments.

[0024] In an embodiment of the printed fabric of the present invention, from the viewpoint of exerting the effects of the present invention, the disperse dye is preferably a sublimation dye, the resin is preferably a polyalkylene oxide or a polyalkylene oxide-polyester copolymer, and the fabric preferably contains cellulose fibers.

[0025] The textile printing method of the present invention is a textile printing method for obtaining the printed textile of the present invention, and is characterized by comprising a step of applying the resin to the textile, a dyeing step of dyeing the resin applied to the textile with the disperse dye, and a step of causing crystal growth of the disperse dye after the dyeing step.

[0026] The printing method of the present invention makes it possible to produce a printed fabric in which the heat resistance of the image printed on the fabric is improved and the texture of the fabric before printing is maintained.

[0027] As an embodiment of the textile printing method of the present invention, from the viewpoint of manifesting the effects of the present invention, it is preferable that the dyeing is carried out by a sublimation transfer method.

[0028] Furthermore, the crystal growth step preferably includes a step of washing the fabric after the dyeing step with a washing solution. Furthermore, from the viewpoint of achieving good crystal growth, the washing is preferably carried out by immersing the fabric after the dyeing step in water. Furthermore, the conditions for immersion in water are preferably an immersion time within the range of 30 to 120 seconds, an immersion temperature during immersion of less than 30°C, etc.

[0029] The present invention, its components, and embodiments and modes for carrying out the present invention will be described below. In this application, the symbol "to" is used to mean that the numerical values ​​before and after it are included as lower and upper limits.

[0030] [Printed fabric] The printed fabric of the present invention is a printed fabric dyed with a disperse dye, characterized in that a dyeable resin is applied to the fabric, the resin is dyed with the disperse dye, and the disperse dye is crystallized.

[0031] The printed fabric of the present invention is obtained by printing an image using a disperse dye on a fabric to which a dyeable resin (hereinafter also referred to as "resin (P)") has been applied. Hereinafter, the fabric to which resin (P) has been applied will also be referred to as a "resin-coated fabric." In a resin-coated fabric, the resin (P) exists, for example, in the form of a layer attached to the surface of the fibers constituting the fabric. Typically, the resin (P) exists so as to coat the surface of each fiber and fill the gaps between the fibers. Alternatively, the resin (P) penetrates into the interior of the fibers constituting the fabric, swells the fibers, and exists inside the swollen fibers.

[0032] A printed fabric is obtained by dyeing the resin (P) in such a resin-attached fabric with a disperse dye. When dyeing the resin (P) with a disperse dye, the disperse dye is present in the matrix of the resin (P) attached to the fabric. In the printed fabric of the present invention, the disperse dye is contained in a crystallized state in the matrix of the resin (P).

[0033] Here, in a printed fabric dyed with a disperse dye, whether or not the disperse dye is crystallized can be determined by the results of X-ray diffraction (XRD) measurements.

[0034] Specifically, X-ray diffraction measurements are performed under the following conditions. ·XRD measurement Equipment: X-ray diffractometer TTR-II (Rigaku Corporation) X-ray: 50kV-300mA(15kW) Optical system: parallel beam method (transmission method) Slit conditions: Divergence slit 1.0 mm, scattering slit open, receiving slit open Measurement conditions: FT Scanning range: 5 to 45° (step width: 0.02°) Coefficient time: 10s Sample preparation: A 20mm x 20mm piece of printed fabric is placed in the sample holder and measured.

[0035] In the obtained measurement results, if a crystallization peak derived from the disperse dye is observed in the XRD spectrum, it is determined that the disperse dye has crystallized in the printed fabric. If no crystallization peak derived from the disperse dye is observed, it is determined that the disperse dye has not crystallized.

[0036] The crystalline peak in the XRD spectrum refers to a peak having a half-width of 0.6 or less.

[0037] In the printed fabric of the present invention, the average particle size of the crystallized disperse dye is preferably 50 nm or more, more preferably 100 nm or more, and even more preferably 150 nm or more. When the average particle size of the disperse dye crystal particles is 50 nm or more, the heat resistance of the printed image on the printed fabric is better.

[0038] Furthermore, the size of the crystal particles of the disperse dye is preferably 10 μm or less, and more preferably 1 μm or less, in terms of an average particle diameter, from the viewpoints of suppressing discoloration of the disperse dye (printed image) and suppressing the disperse dye from falling off and causing a decrease in density of the printed image.

[0039] The average particle size of the crystal particles of the disperse dye can be determined, for example, from an electron microscope photograph of the cross section of the printed fabric. The average particle size is the average of the 10 largest diameter crystal particles.

[0040] The components of the printed fabric of the present invention will be described below.

[0041] [Fabric] The material of the fibers constituting the fabric of the present invention is not particularly limited, and examples thereof include natural fibers (hydrophilic fibers) such as cellulose fibers (natural cotton), hemp, wool, and silk, and chemical fibers such as rayon, vinylon, nylon, acrylic, polyurethane, polyester, and acetate.

[0042] The fabric preferably contains natural fibers such as cellulose fibers, hemp, wool, and silk, and it is particularly preferable that the fabric contains cellulose fibers because the effects of the present invention can be significantly exhibited. The fabric may be made of one type of natural fiber or two or more types. When the fabric contains natural fibers, it may further contain one or more types of chemical fibers.

[0043] The fabric may be any form of fabric, such as woven fabric, nonwoven fabric, or knitted fabric, made from these fibers. The fabric may also be a blended woven fabric or blended nonwoven fabric made from two or more types of fibers. As described above, the fabric preferably contains cellulose fibers. When the fabric contains cellulose fibers and fibers other than cellulose fibers, the other fibers preferably contain polyester fibers.

[0044] The ratio of natural fibers and chemical fibers in the fibers constituting the fabric is expressed as the mass % of natural fibers and the mass % of chemical fibers contained relative to the total amount of the fabric (total amount of natural fibers and chemical fibers). When the fabric of the present invention contains natural fibers and optionally chemical fibers, the ratio of natural fibers in the fabric is preferably in the range of 5 to 100 mass % and the ratio of chemical fibers is preferably in the range of 0 to 95 mass %. For example, when the fabric contains cellulose fibers and polyester fibers, the ratio of cellulose fibers is preferably in the range of 35 to 100 mass % and the ratio of polyester fibers is preferably in the range of 0 to 65 mass %.

[0045] [Dyeable resin (Resin (P)] The resin (P) is preferably a resin that can be dyed with a disperse dye, which will be described later. Depending on the type of fabric and the type of disperse dye, examples of the resin (P) include a hydrophobic resin, a hydrophilic resin, and a hydrophilic / hydrophobic resin having a hydrophobic moiety and a hydrophilic moiety.

[0046] For example, when the fibers constituting the fabric include chemical fibers, the resin (P) is preferably a hydrophobic resin. When the fibers constituting the fabric include natural fibers, such as cellulose fibers, the resin (P) is preferably a hydrophilic resin or a hydrophilic / hydrophobic resin, and particularly preferably a polyalkylene oxide or a polyalkylene oxide-polyester copolymer.

[0047] (hydrophobic resin) Hydrophobic resins are primarily used when the fabric contains hydrophobic fibers such as polyester fibers. Examples of hydrophobic resins used in the present invention include polyester resins, fluororesins such as polytetrafluoroethylene (PTFE), polyolefin resins such as polyisobutylene, polyethylene, polyisoprene, and polybutadiene, polystyrene resins, (meth)acrylic resins such as polylauryl methacrylate, polystearyl methacrylate, polyisobornyl methacrylate, poly-t-butyl methacrylate, polyethyl (meth)acrylate, and polymethyl (meth)acrylate, and polyvinyl chloride. Among these, polyester resins are preferred. Note that "(meth)acrylic" refers to either methacrylic or acrylic.

[0048] A polyester resin is a resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (a polycarboxylic acid compound) and a divalent or higher alcohol (a polyhydric alcohol compound). A polyester resin obtained by reacting a dicarboxylic acid with a diol is preferred. In this case, the polyester resin contains a polymerization unit derived from the dicarboxylic acid and a polymerization unit derived from the diol. Hereinafter, the polymerization unit may be simply referred to as a "unit."

[0049] <Units derived from dicarboxylic acids> The dicarboxylic acid in the dicarboxylic acid-derived unit may be an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, or an aromatic dicarboxylic acid, without any particular limitation. When the fabric contains polyester fibers, the dicarboxylic acid preferably contains an aromatic dicarboxylic acid, from the viewpoint of enhancing affinity with the fabric.

[0050] Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid (orthophthalic acid), naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, etc., with terephthalic acid being preferred.

[0051] These aromatic dicarboxylic acids may further have an anionic group (for example, a carboxy group, a sulfonyl group, etc.) Examples of aromatic dicarboxylic acids having an anionic group include trimellitic acid, sulfoterephthalic acid, sulfoisophthalic acid, sulfophthalic acid, etc.

[0052] The units derived from aromatic dicarboxylic acids may account for 5 to 100 mol %, preferably 10 to 100 mol %, based on the total number of moles of units derived from dicarboxylic acids.

[0053] The units derived from dicarboxylic acids may further contain units derived from other dicarboxylic acids as needed. Examples of other dicarboxylic acids include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and cyclopentanedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, succinic acid, oxalic acid, and sebacic acid.

[0054] <Units derived from diols> The diol in the diol-derived unit may be an aliphatic diol, an alicyclic diol, or an aromatic diol, without any particular limitation. When the fabric contains polyester fibers, the diol preferably contains an aliphatic diol, from the viewpoint of enhancing affinity with the fabric.

[0055] The aliphatic diol is preferably an aliphatic diol having 1 to 10 carbon atoms, preferably 1 to 4. Examples of such aliphatic diols include alkylene diols such as ethylene glycol, trimethylene glycol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol, and ethylene glycol is preferred.

[0056] The aliphatic diol may further have an anionic group, as described above. Examples of the aliphatic diol having an anionic group include N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (CAS number: 10191-18-1), dimethylolpropionic acid, and dimethylol.

[0057] The units derived from the aliphatic diol can be 5 to 100 mol %, preferably 10 to 100 mol %, based on the total number of moles of the units derived from the diol.

[0058] The units derived from the diol may further contain units derived from a diol other than those mentioned above, if necessary. Examples of the other diol include aromatic diols such as xylylene glycol and alicyclic diols such as cyclohexanedimethanol.

[0059] The weight-average molecular weight of the hydrophobic resin is not particularly limited, but is preferably in the range of 500 to 10,000. When the weight-average molecular weight of the hydrophobic resin is 500 or more, the properties of the hydrophobic resin are easily expressed, and the affinity with disperse dyes is easily increased. When the weight-average molecular weight of the hydrophobic resin is 10,000 or less, the texture of the fabric is less likely to be impaired.

[0060] Furthermore, as will be described later, when used as a block copolymer of a hydrophobic block derived from a hydrophobic resin and a hydrophilic block derived from a hydrophilic resin, the crystallinity is not too high, so that the penetration and dyeing ability of the disperse dye are not easily impaired during heating in the color development step (thermal transfer step). From the same viewpoint, it is more preferable that the weight-average molecular weight of the hydrophobic resin is within the range of 500 to 5,000.

[0061] The weight average molecular weight of the hydrophobic resin can be measured by gel permeation chromatography in terms of polystyrene.

[0062] Specifically, measurements can be performed using a high-performance liquid chromatograph (Waters 2695 (main unit) and Waters 2414 (detector) manufactured by Water Japan) equipped with three columns (Shodex (registered trademark) GPCKF-806L (exclusion limit molecular weight: 2 × 107, separation range: 100 to 2 × 107, theoretical plate number: 10,000 plates / column, packing material: styrene-divinylbenzene copolymer, packing particle size: 10 μm)) arranged in series.

[0063] The hydrophobic resin preferably has higher crystallinity than the hydrophilic resin and may have a higher glass transition temperature Tg or melting point Tm than the hydrophilic resin. For example, the Tg of the hydrophobic resin may be 50 to 110° C. The Tg of the hydrophilic resin may be measured by the same method as the method for measuring the Tg of a block copolymer described below.

[0064] (hydrophilic resin) The hydrophilic resin is mainly used when the fabric contains hydrophilic fibers such as cellulose fibers. Examples of the hydrophilic resin according to the present invention include polyalkylene oxide, polyvinyl alcohol, polyamide, polyacrylonitrile, polyvinylpyrrolidone, polyurethane resin, etc., and polyalkylene oxide is preferred.

[0065] The polyalkylene oxide is a polymer obtained by ring-opening and addition polymerization of an alkylene oxide, and the alkylene oxide preferably has 2 to 6 carbon atoms. Examples of polyalkylene oxides include polyethylene oxide (PEO), polypropylene oxide (PPO), polytrimethylene oxide, polytetramethylene oxide, polyhexamethylene oxide, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide adduct of polypropylene oxide, and a copolymer of ethylene oxide and tetrahydrofuran. Among these, PEO is preferred from the viewpoint of its high affinity with fabrics containing hydrophilic fibers such as cellulose fibers and easy bonding.

[0066] The weight-average molecular weight of the hydrophilic resin is not particularly limited, but is preferably within the range of 500 to 6000. When the weight-average molecular weight of the hydrophilic resin is 500 or more, the properties of the hydrophilic resin are easily exhibited, and therefore, as will be described later, when used as a block copolymer of a hydrophobic block derived from a hydrophobic resin and a hydrophilic block derived from a hydrophilic resin, the resin is easily and satisfactorily bound to a fabric containing hydrophilic fibers such as cellulose fibers.

[0067] When the weight-average molecular weight of the hydrophilic resin is 6000 or less, the texture of the fabric is less likely to be impaired. From the same viewpoint, the weight-average molecular weight of the hydrophilic resin is more preferably within the range of 500 to 5000. The weight-average molecular weight of the hydrophilic resin can be measured in the same manner as the weight-average molecular weight of the hydrophobic resin described above.

[0068] As described above, the hydrophilic resin preferably has lower crystallinity than the hydrophobic resin, and may have a lower glass transition temperature Tg or melting point Tm than the hydrophobic resin. For example, the Tg or Tm of the hydrophilic resin may be −110 to 60° C. The hydrophilic resin is preferably an amorphous resin, and preferably does not substantially have a melting point.

[0069] (hydrophilic / hydrophobic resin) Hydrophilic / hydrophobic resins are used when both hydrophilic and hydrophobic properties are required in a dyeable resin, and are preferably used, for example, when the disperse dye is hydrophobic and the fabric contains hydrophilic fibers such as cellulose fibers.

[0070] The hydrophilic / hydrophobic resin is preferably a block copolymer (hereinafter also referred to as "block copolymer (A)") having a hydrophobic block derived from the hydrophobic resin and a hydrophilic block derived from the hydrophilic resin. In the block copolymer (A), the hydrophobic block is preferably derived from a polyester resin, and the hydrophilic block is preferably derived from a polyalkylene oxide. As the block copolymer (A), a polyalkylene oxide-polyester copolymer is particularly preferred.

[0071] In the block copolymer (A), the relationship between the SP value (SPB) of the hydrophilic resin constituting the hydrophilic block and the SP value (SPA) of the hydrophobic resin constituting the hydrophobic block is preferably SPB > SPA. Furthermore, the difference ΔSP between SPB and SPA (SPB - SPA) is preferably 1.0 or greater. When ΔSP is 1.0 or greater, the hydrophilic block has a high affinity for fabrics containing hydrophilic fibers such as natural fibers, which facilitates the adhesion of the block copolymer (A) to the fabric. Furthermore, the hydrophobic block has an affinity for disperse dyes that exhibit hydrophobicity, which facilitates the penetration and fixation of the disperse dyes into the fabric. From the same perspective, ΔSP is more preferably 2.0 or greater.

[0072] The SP value is called the solubility parameter. The SP value of the resin material in the present invention can be determined from the molecular attractive constant, that is, from the molecular attractive constant (G) and the molar volume (V) of each functional group or atomic group constituting the resin molecule, by the formula SP value = ΣG / V (DASmall, J. Appl. Chem., 3, 71, (1953), KL Hoy, J. Paint Technol., 42, 76 (1970)).

[0073] As the block copolymer (A), a block copolymer having a hydrophobic block derived from a hydrophobic resin having an SP value of less than 11 and a hydrophilic block derived from a hydrophilic resin having an SP value of 11 or more (hereinafter also referred to as "block copolymer (A1)") is particularly preferred.

[0074] When the block copolymer (A1) contains two or more types of at least one of hydrophobic blocks and hydrophilic blocks, the ΔSP value is preferably the difference between the SP value of the hydrophobic block with the maximum SP value among the hydrophobic blocks with an SP value of less than 11 and the SP value of the hydrophilic block with the minimum SP value among the hydrophilic blocks with an SP value of 11 or more.

[0075] The hydrophobic block in the block copolymer (A1) is a block derived from a hydrophobic resin having an SP value of less than 11. Such a hydrophobic block has an affinity for disperse dyes, and can therefore facilitate the penetration and fixation of disperse dyes into fabrics (via the block copolymer).

[0076] From the viewpoint of further enhancing affinity with disperse dyes, it is preferable that a hydrophobic resin having an SP value of less than 11 not only has a ΔSP satisfying the above range, but also has a difference of a certain level or less (for example, ±2 or less) from the SP value of the disperse dye. For example, the SP value of the hydrophobic resin constituting the hydrophobic block is preferably 8.7 or more and less than 11, more preferably 9.5 or more and less than 11, and even more preferably 10.2 or more and less than 11.

[0077] Furthermore, the hydrophobic resin having an SP value of less than 11 is preferably a resin having higher crystallinity than the hydrophilic resin, and more preferably a crystalline resin. A crystalline resin usually has a melting point.

[0078] Examples of hydrophobic resins having an SP value of less than 11 include the following hydrophobic resins among the above-mentioned hydrophobic resins.

[0079] These include polyester (but with an SP value of less than 11), PTFE (SP value: 6.2), polyisobutylene (SP value: 7.7), polyethylene (SP value: 8.1), polyisoprene (SP value: 8.15), polylauryl methacrylate (SP value: 8.2), polystearyl methacrylate (SP value: 8.2), polyisobornyl methacrylate (SP value: 8.2), poly-t-butyl methacrylate (SP value: 8.2), polybutadiene (SP value: 8.4), polystyrene (SP value: 9.1), polyethyl methacrylate (SP value: 9.1), polyethyl acrylate (9.2), polymethyl methacrylate (9.3), polymethyl acrylate (SP value: 9.7), and polyvinyl chloride (SP value: 10.1).

[0080] Of these, the hydrophobic resin is preferably polyester (however, the SP value is less than 11). As the polyester, polyethylene terephthalate (PET) (SP value: 10.7) and the like are preferable.

[0081] The hydrophilic block in the block copolymer (A1) is a block derived from a hydrophilic resin having an SP value of at least 11. Such a hydrophilic block has a high affinity with fabrics containing hydrophilic fibers such as natural fibers, and can therefore enhance the binding ability of the block copolymer to fabrics.

[0082] A hydrophilic resin with an SP value of 11 or more preferably has an SP value of 11 or more and is within ±2 of the SP value of the fibers constituting the fabric, for example, the hydrophilic fibers, more preferably ±1.0 or less, and even more preferably ±0.5 or less. When the fibers constituting the fabric are cellulose fibers with an SP value of 15.7, the SP value of the hydrophilic resin constituting the hydrophilic block is preferably 13.7 to 17.7, more preferably 14.7 to 16.7, and even more preferably 15.2 to 16.2.

[0083] Furthermore, the hydrophilic resin having an SP value of 11 or more is preferably a resin with lower crystallinity than the hydrophobic resin, and more preferably an amorphous resin. When the hydrophilic block is an amorphous resin, the resulting image-formed product is less likely to harden and the texture is less likely to be impaired. Furthermore, such a hydrophilic block is easily softened by heating and tends to increase the free volume, which makes it easier for the disperse dye to penetrate further into the fabric by heating in the color-developing process. The amorphous resin has essentially no melting point.

[0084] Examples of hydrophilic resins having an SP value of 11 or more include the following hydrophilic resins among the above-mentioned hydrophilic resins.

[0085] Examples include polyalkylene oxide (SP value: 11.0 to 15.0), polyvinyl alcohol (SP value: 12.6), polyamide (SP value: 13.6), polyacrylonitrile (SP value: 14.8), and polyvinylpyrrolidone.

[0086] Among them, the hydrophilic resin is preferably polyalkylene oxide (SP value: 11.0 to 15.0). Preferred polyalkylene oxides include PEO (SP value: 15.0) and PPO (SP value: 15.0).

[0087] The content of the hydrophobic block in the block copolymer (A) by mass is preferably smaller than the content of the hydrophilic block by mass, specifically, the contents of the hydrophobic block and the hydrophilic block are preferably 5 to 40 mass% and 60 to 95 mass%, respectively, based on the total content of the hydrophobic block and the hydrophilic block.

[0088] When the content of the hydrophobic block is 5% by mass or more, the block copolymer (A) has a higher affinity with the disperse dye (through the hydrophobic block), which facilitates an improvement in the penetration and fixation of the disperse dye into fabrics. On the other hand, when the content of the hydrophilic block is 95% by mass or less, the content of the hydrophobic block is not too small, which prevents a decrease in the affinity with the disperse dye, and prevents a decrease in the penetration and fixation of the disperse dye into fabrics.

[0089] When the content of the hydrophilic block is 60% by mass or more, the binding ability of the block copolymer (A) to fabrics containing hydrophilic fibers such as natural fibers is easily improved.When the content of the hydrophobic block is 40% by mass or less, the content of the hydrophilic block is not too small, so that the binding ability of the block copolymer to fabrics is not easily impaired.

[0090] From the same viewpoint, the contents of the hydrophobic block and the hydrophilic block in the block copolymer (A) are preferably 10 to 30% by mass and 70 to 90% by mass, respectively, based on the total content of the hydrophobic block and the hydrophilic block.

[0091] The block copolymer (A) has the above-mentioned hydrophobic block and hydrophilic block, but preferably does not have a urethane bond, because resins having a urethane bond are prone to lose their fixability to fabrics due to photodegradation.

[0092] The weight-average molecular weight of the block copolymer (A) is not particularly limited, but is preferably, for example, 1,000 to 30,000. When the weight-average molecular weight of the block copolymer (A) is 1,000 or more, the binding ability of the block copolymer (A) to the fabric is easily increased, and when it is 30,000 or less, the fabric is less likely to become stiff and the texture is less likely to be impaired. From the same viewpoint, the weight-average molecular weight of the block copolymer (A) is more preferably 2,000 to 25,000.

[0093] The glass transition temperature Tg or melting point Tm of the block copolymer (A) is not particularly limited, but is preferably less than 30° C. A block copolymer (A) having a Tg or Tm of less than 30° C. has appropriate flexibility, and therefore is less likely to prevent the disperse dye from penetrating into the resin-coated fabric when an ink containing a disperse dye is applied to the resin-coated fabric and fixed.

[0094] For example, in transfer printing, ink on a transfer medium is placed on the surface of a resin-coated fabric and transferred by heat and pressure bonding. The heat generated during heat and pressure bonding tends to soften the block copolymer (A), which can lessen the barrier to the penetration of the disperse dye into the resin-coated fabric. This improves the dyeability of the disperse dye and facilitates further improvement of fixability. From the same perspective, the Tg or Tm of the block copolymer (A) is more preferably −20° C. or higher and lower than 25° C., and even more preferably 0 to 20° C.

[0095] The Tg or Tm of the block copolymer (A) can be determined by reading the glass transition temperature Tg or Tm from the endothermic peak when the block copolymer (A) is heated at a rate of 10°C / min in a temperature range of -30 to 100°C using a DSC (differential scanning calorimeter).

[0096] The Tg or Tm of the block copolymer (A) can be adjusted, for example, by the content ratio of the hydrophilic block to the hydrophobic block, etc. In order to lower the Tg or Tm of the block copolymer (A), it is preferable to increase the content ratio of the hydrophilic block, for example, although this depends on the types of resins constituting the hydrophilic block and the hydrophobic block.

[0097] The resin-coated fabric according to the present invention is obtained by applying a resin (P) to the above-mentioned fabric. The method for applying the resin (P) to the fabric can be carried out, for example, in the same manner as the step of applying the resin (P) to the fabric in the printing method of the present invention described below. The form of the resin-coated fabric is as described above.

[0098] The amount of resin (P) applied to the fabric is, for example, 1 to 40 g / m 2 The range is preferably 3 to 30 g / m 2 When the amount of resin (P) applied to the fabric is within the above range, dyeing with disperse dyes is carried out sufficiently and there is almost no risk of the texture of the fabric being impaired.

[0099] (dispersible dye) Disperse dyes are dyes that are insoluble or slightly soluble in water. As disperse dyes, sublimation dyes that are insoluble or slightly soluble in water and have the property of sublimating upon heating are preferred. Here, "insoluble or slightly soluble in water" means that the solubility in water at 25°C is 10 mg / L or less, preferably 5 mg / L or less, and more preferably 1 mg / L or less.

[0100] The type of disperse dye is not particularly limited, and includes azo dyes, anthraquinone dyes, etc. Specifically, examples of sublimation dyes among disperse dyes include the following dyes.

[0101] CIDisperseYellow3, 4, 5, 7, 9, 13, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58 ,60,63,64,66,68,71,74,76,79,82,83,85,86,88,90,91,93,98,99,100,104 , 114, 116, 118, 119, 122, 124, 126, 135, 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224, etc.

[0102] CIDisperseOrange1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 47, 48, 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130, 139, 142, etc.

[0103] CIDisperseRed1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 14 6, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 227, 229, 239, 240, 257, 258, 277, 278, 279, 281, 288, 289, 298, 302, 303, 310, 311, 312, 320, 324, 328, etc.

[0104] CIDisperseViolet1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63, 69, 77, etc.

[0105] CIDisperseGreen9 etc. CIDisperseBrown1, 2, 4, 9, 13, 19 etc.

[0106] CIDisperseBlue3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79, 81, 82 , 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 139, 141, 142, 143, 146 , 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207, 211, 214, 224, 225, 257, 259, 267, 268, 270, 284, 285, 287, 288, 291, 293, 295, 297, 301, 315, 330, 333, etc. CIDisperseBlack1, 3, 10, 24 etc.

[0107] The molecular weight of the disperse dye is not particularly limited, but for example, when an ink applied to a transfer medium is transferred to a resin-coated fabric as described below to form an image (sublimation printing), the molecular weight is preferably small (e.g., 200 to 350) from the viewpoint of facilitating sublimation of the disperse dye. On the other hand, the molecular weight is preferably moderately large (e.g., 350 to 500) from the viewpoint of preventing the disperse dye from escaping from the fabric.

[0108] In the printed fabric of the present invention, the disperse dye is present in a crystallized state in the matrix of the resin (P) attached to the fabric. The degree of crystallization of the disperse dye is not particularly limited as long as it satisfies the above-mentioned criteria. The degree of crystallization of the disperse dye can be determined by the size of the crystal particles of the disperse dye. The size of the crystal particles of the disperse dye is preferably within the above-mentioned range. The amount of the disperse dye in the printed fabric of the present invention is appropriately selected depending on the color tone of the image to be printed.

[0109] The printed fabric of the present invention may have other components in addition to the structure in which the disperse dye is crystallized and present in the resin matrix of the resin-coated fabric, as long as the effects of the present invention are not impaired. However, it is preferable that the printed fabric does not have, as another component, for example, a resin coating layer formed to cover the resin-coated fabric after dyeing. This is because if the printed fabric has a resin coating layer, the texture of the fabric before printing may be impaired, and further, the crystallized disperse dye may melt or sublimate when the resin coating layer is formed.

[0110] As explained above, in the printed fabric of the present invention, the disperse dye applied to correspond to the desired image is crystallized in the matrix of the resin (P) applied to the fabric, thereby improving the heat resistance of the image printed on the fabric. Furthermore, the simple structure of the printed fabric of the present invention prevents changes in the texture of the fabric before and after printing.

[0111] [Printing method] The textile printing method of the present invention is a method for printing a fabric to obtain the printed fabric of the present invention, and is characterized by comprising the following steps (1) to (3): (1) A step of applying a dyeable resin (resin (P)) to fabric (hereinafter also referred to as the “pretreatment step”) (2) A dyeing step in which the resin (P) applied to the fabric is dyed with a disperse dye. (3) After the dyeing process, a process of growing crystals of the disperse dye (hereinafter also referred to as the "crystal growth process") Each step will be described below.

[0112] (1) Pretreatment process The pretreatment step is a step of applying a resin (P) to a fabric to obtain a resin-coated fabric. The application of the resin (P) to the fabric is carried out, for example, by applying a pretreatment liquid containing the resin (P) and a liquid medium to the fabric. After application, the liquid medium is removed from the coating of the pretreatment liquid applied to the fabric to obtain a resin-coated fabric.

[0113] <Pretreatment liquid> The pretreatment liquid typically contains a resin (P) and a liquid medium.

[0114] (Resin (P)) The resin (P) is as described above. The content of the resin (P) in the pretreatment liquid is not particularly limited, but is preferably 2 to 60% by mass relative to the pretreatment liquid. When the content of the resin (P) is 2% by mass or more, it is easy to ensure that the amount of resin (P) applied (adhered amount) is sufficient, making it easy to increase image density, and when it is 60% by mass or less, the amount applied to the fabric is not too great, making it difficult to impair the texture of the fabric. From the same perspective, the content of the resin (P) is more preferably 5 to 20% by mass relative to the pretreatment liquid.

[0115] (liquid medium) The liquid medium is preferably water. The water is not particularly limited and may be ion-exchanged water, distilled water, or pure water. The water content in the pretreatment liquid is preferably 40 to 98% by mass, more preferably 80 to 95% by mass.

[0116] The pretreatment liquid may contain, as a liquid medium, other solvents in addition to water. The other solvents are not particularly limited, but are preferably water-soluble organic solvents from the viewpoints of moisture retention and viscosity adjustment. In particular, when the pretreatment liquid is applied to fabric by an inkjet method, the pretreatment liquid preferably contains a water-soluble organic solvent. When the liquid medium contains a water-soluble organic solvent in addition to water, the total content of water and the water-soluble organic solvent is preferably 40 to 98% by mass, more preferably 80 to 95% by mass, of the pretreatment liquid.

[0117] Examples of the water-soluble organic solvent include alcohols (e.g., methanol, ethanol, propanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol), polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, glycerin, and compounds represented by the following formula (1)), polyhydric alcohol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether), ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether), amines (e.g., ethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine), amides (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide), heterocycles (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidine), sulfoxides (e.g., dimethyl sulfoxide), sulfones (e.g., sulfolane).

[0118] [ka]

[0119] [In formula (1), R 11 represents an ethylene glycol group or a propylene glycol group, x, y, and z are all positive integers, and x+y+z=3 to 30.]

[0120] In particular, when the fabric contains hydrophilic fibers such as cellulose fibers, the pretreatment liquid preferably contains a water-soluble organic solvent that has a high affinity for hydrophilic fibers, from the viewpoint of promoting penetration of the pretreatment liquid into the fabric. Such water-soluble organic solvents are preferably polyhydric alcohols having a molecular weight of 400 to 1000, such as polyethylene glycol having a molecular weight of 400 to 1000, polypropylene glycol having a molecular weight of 400 to 1000, glycerin, and compounds represented by formula (1), and more preferably glycerin.

[0121] The content of the polyhydric alcohols may be 25 to 100% by mass, preferably 50 to 100% by mass, based on the water-soluble organic solvent, and the content of the water-soluble organic solvent may be 10 to 50% by mass, preferably 20 to 40% by mass, based on the pretreatment liquid.

[0122] (Other ingredients) The pretreatment liquid according to the present invention may further contain other components in addition to those described above, if necessary. Examples of such other components include preservatives, pH adjusters, etc.

[0123] Examples of preservatives include aromatic halogen compounds (eg, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (eg, PROXELGXL), and the like.

[0124] Examples of pH adjusters include citric acid, sodium citrate, hydrochloric acid, sodium hydroxide, and the like.

[0125] (Physical properties of pretreatment liquid) The viscosity of the pretreatment liquid at 25°C can be adjusted as appropriate depending on the method of application to the fabric. For example, when the pretreatment liquid is applied by an inkjet method, the viscosity of the pretreatment liquid is preferably 4 to 20 mPa s. The viscosity of the pretreatment liquid can be measured at 25°C using an E-type viscometer.

[0126] <Application of pre-treatment liquid> In the pretreatment step, the pretreatment liquid is applied to at least a portion of the surface of the fabric. The pretreatment liquid may be applied to the entire surface of the fabric, or may be applied selectively to only the area to be dyed with a disperse dye according to the image to be printed.

[0127] As a method for applying the pretreatment liquid to the fabric, any known method can be used without any particular limitation. Specific examples include a spray method, a mangle method (a pad method or a dipping method), a coating method, an inkjet method, etc. For example, in the dyeing step described below, the inkjet method is preferred from the viewpoint of being able to perform the application of the ink containing a disperse dye continuously, and the mangle method or the coater method is preferred from the viewpoint of applying a predetermined amount of the pretreatment liquid in a short time.

[0128] In the mangle method, a fabric is immersed in a pretreatment liquid stored in a bath, and then the amount of pretreatment liquid applied is adjusted by squeezing. The temperature of the pretreatment liquid is not particularly limited, but can be set to 15 to 30°C. The conditions for applying ink in the inkjet method can be the same as those for applying ink in the dyeing process.

[0129] The amount of the pretreatment liquid to be applied is not particularly limited and can be adjusted depending on the content of the resin (P) in the pretreatment liquid, the amount of ink to be applied, etc. The amount of the pretreatment liquid to be applied is set, for example, so that the amount of the resin (P) to be applied falls within the above-mentioned range.

[0130] <Drying of pre-treatment liquid> After applying the pretreatment liquid to the fabric, it is preferable to remove the liquid medium from the coating film of the pretreatment liquid applied to the fabric, i.e., to dry it. The drying method is not particularly limited, and it is preferable to use hot air, a hot plate, or heating with a heat roller. From the viewpoint of sufficiently removing the liquid medium in a short time, heat drying is more preferable. The drying temperature is preferably in the range of 100 to 130°C.

[0131] (2) Dyeing process The dyeing step is a step of dyeing the resin (P) applied to the fabric with a disperse dye. Specifically, the dyeing step is carried out on the resin-coated fabric obtained above using an ink containing a disperse dye and a liquid medium.

[0132] (ink) Inks typically contain a disperse dye and a liquid medium.

[0133] The disperse dye is as described above. However, the disperse dye contained in the ink may or may not be crystallized. Dyeing methods using ink include a direct printing method in which the ink is applied directly to the surface of a resin-coated fabric (a surface treated with a pretreatment liquid (pretreated surface)), and a transfer printing method (sublimation transfer method) in which the ink is applied to a transfer medium and then the ink is transferred from the transfer medium to the surface of the resin-coated fabric (pretreated surface) to perform printing. An example of a method for applying ink to an object, such as a coating method, is the inkjet method, which enables high-precision printing.

[0134] The average particle size of the dispersible dye in the ink is not particularly limited, but from the viewpoint of ejection stability by the inkjet method, it may be, for example, 300 nm or less. The average particle size can be determined by a commercially available particle size measuring device using a light scattering method, an electrophoresis method, a laser Doppler method, or the like, and examples of particle size measuring devices include the Zetasizer 1000 manufactured by Malvern Instruments.

[0135] The content of disperse dye in the ink is not particularly limited, but is preferably in the range of 2 to 10% by mass of the ink. If the content of disperse dye is 2% by mass or more, it is easy to form a high-density image, and if it is 10% by mass or less, the viscosity of the ink does not become too high, so ejection stability is less likely to be impaired. From the same perspective, the content of disperse dye is more preferably in the range of 5 to 10% by mass of the ink.

[0136] (liquid medium) The liquid medium is preferably water. The water may be ion-exchanged water, distilled water, or pure water. The water content in the pretreatment liquid is preferably 90 to 98% by mass, more preferably 90 to 95% by mass.

[0137] The ink may contain, as a liquid medium, other solvents in addition to water. The other solvents are not particularly limited, but are preferably water-soluble organic solvents. The water-soluble organic solvents may be the same as those used in the pretreatment liquid. When the liquid medium contains a water-soluble organic solvent in addition to water, the total content of water and the water-soluble organic solvent is preferably 90 to 98% by mass, and more preferably 90 to 95% by mass, based on the ink.

[0138] Among water-soluble organic solvents, those that do not easily thicken upon drying are preferred from the viewpoints of facilitating penetration of the ink into the interior of the resin-coated fabric and preventing loss of ejection stability in inkjet printing. Therefore, the ink preferably contains a high-boiling-point solvent with a boiling point of 200°C or higher.

[0139] The high-boiling solvent having a boiling point of 200°C or higher may be any water-soluble organic solvent having a boiling point of 200°C or higher, and is preferably a polyol or a polyalkylene oxide. Examples of polyols having a boiling point of 200°C or higher include dihydric alcohols such as 1,3-butanediol (boiling point 208°C), 1,6-hexanediol (boiling point 223°C), and polypropylene glycol; and trihydric or higher alcohols such as glycerin (boiling point 290°C) and trimethylolpropane (boiling point 295°C). Examples of polyalkylene oxides having a boiling point of 200°C or higher include ethers of dihydric alcohols such as diethylene glycol monoethyl ether (boiling point 202°C), triethylene glycol monomethyl ether (boiling point 245°C), tetraethylene glycol monomethyl ether (boiling point 305°C), tripropylene glycol monoethyl ether (boiling point 256°C), and polypropylene glycol, as well as ethers of trihydric or higher alcohols such as glycerin (boiling point 290°C) and hexanetriol.

[0140] The content of the water-soluble organic solvent is preferably within the range of 20 to 70% by mass of the ink. When the content of the water-soluble organic solvent is 20% by mass or more, the dispersibility and ejection properties of the disperse dye are more likely to be improved, and when it is 70% by mass or less, the drying properties of the ink are less likely to be impaired.

[0141] (Other ingredients) The ink may further contain other components as needed, such as dispersants, preservatives, and pH adjusters.

[0142] (dispersant) The dispersant can be selected depending on the type of disperse dye. Examples of dispersants include formalin condensation products of sodium creosote oil sulfonate, formalin condensation products of sodium cresol sulfonate and sodium 2-naphthol-6-sulfonate, formalin condensation products of sodium cresol sulfonate, formalin condensation products of sodium phenolsulfonate, formalin condensation products of sodium β-naphtholsulfonate, formalin condensation products containing sodium β-naphthalenesulfonate and sodium β-naphtholsulfonate, alkylene oxides including ethylene oxide and propylene oxide, alkylatable compounds including fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, and carboxylic acid amines, lignin sulfonates, sodium paraffin sulfonate, copolymers of α-olefins and maleic anhydride, and known comb-type block polymers.

[0143] Examples of comb block polymers include DISPERBYK-190, DISPERBYK-194N, DISPERBYK-2010, DISPERBYK-2015, and BYK-154 manufactured by BYK-Chemie ("DISPERBYK" and "BYK" are registered trademarks of the company).

[0144] The content of the dispersant is not particularly limited, but is preferably in the range of 20 to 200 parts by mass relative to 100 parts by mass of the disperse dye. When the content of the dispersant is 20 parts by mass or more, the dispersibility of the disperse dye is likely to be further improved, and when it is 200 parts by mass or less, it is easy to suppress the decrease in ejection property due to the dispersant.

[0145] (preservatives, pH adjusters) The preservatives and pH adjusters that can be used are the same as those that can be used in the pretreatment liquid.

[0146] (Ink properties) The viscosity of the ink at 25°C is not particularly limited as long as it provides good ejection properties using an inkjet system, but is preferably in the range of 3 to 20 mPa·s, and more preferably in the range of 4 to 12 mPa·s. The viscosity of the ink can be measured at 25°C using an E-type viscometer.

[0147] <Staining> In the dyeing step, the dyeing method using the ink may be a direct printing method or a transfer printing method (sublimation transfer method), and from the viewpoint of achieving the effects of the present invention, the transfer printing method (sublimation transfer method) is preferred.

[0148] (Direct printing) In direct printing, ink is directly applied to the surface (pre-treated surface) of the resin-coated fabric in accordance with the print image by a known ink application method, for example, an inkjet system. Specifically, in the inkjet system, an inkjet recording device is used to eject ink droplets from an inkjet recording head toward the surface (pre-treated surface) of the resin-coated fabric.

[0149] The temperature of the surface of the resin-coated fabric (pre-treated surface) when the ink droplets land is not particularly limited, but may be heated to a range of 35 to 70°C from the viewpoint of suppressing bleeding of the image before color development.

[0150] On the surface (pre-treated surface) of the resin-coated fabric, a layer of resin (P) is present on the surface of the fibers that make up the fabric. When ink is applied to the surface (pre-treated surface) of such a resin-coated fabric, an ink coating film corresponding to the printed image is formed on the layer of resin (P). Then, by heating this ink coating film, the disperse dye is dyed into the resin (P) and colored, thereby printing the desired image on the fabric. At this time, the disperse dye is diffused in the matrix of the resin (P) in a substantially molecular state.

[0151] The heating method may be a conventionally known method, and is appropriately selected depending on the types of ink, resin (P), and fabric. Examples include steaming with steam; baking with dry heat, thermosol; HT steamer with superheated steam; and heat pressing. Among these, the steaming method, baking method, and heat pressing method are preferred.

[0152] The heating temperature varies depending on the heating method, but from the viewpoint of strengthening the dyeing of the disperse dye to the resin-attached fabric, specifically to the resin (P) applied to the fabric, it is preferably 95°C or higher and lower than 220°C, more preferably 95 to 190°C, and even more preferably 100 to 180°C.

[0153] In direct printing, other steps may be further carried out as necessary. For example, after applying the ink, a preliminary drying step may be carried out to dry the ink applied to the resin-coated fabric before heating.

[0154] (transfer printing) In transfer printing, first, ink is applied to a transfer medium by a known ink application method, for example, an inkjet system, and then dried to form an ink layer (transfer image) corresponding to the printed image. In transfer printing, an ink containing a sublimation dye as a dispersible dye is used.

[0155] The transfer medium used in the present invention is not particularly limited as long as it is capable of forming an ink layer on the surface of the transfer medium and further capable of transferring the ink layer to a resin-coated fabric, for example, it is a medium that does not interfere with the sublimation of the sublimation dye during transfer. For example, the transfer medium is preferably paper on the surface of which an ink-receiving layer is formed of inorganic fine particles such as silica, and examples of the transfer medium include dedicated paper for inkjet printing and transfer paper.

[0156] Next, the surface of the transfer image on the transfer medium is brought into contact with the surface (pre-treated surface) of the resin-coated fabric and heated (heat pressed). This causes the sublimation dye, which is a disperse dye in the transfer image formed on the transfer medium, to be sublimated and transferred to the resin-coated fabric, specifically, to the resin (P) applied to the fabric, thereby printing the desired image on the fabric. The disperse dye (sublimation dye) thus sublimated and transferred to the resin (P) is diffused in the matrix of the resin (P) in a substantially molecular state.

[0157] The transfer temperature (heat press temperature) depends on the sublimation temperature of the sublimation dye used as the dispersible dye, but is preferably within the range of, for example, 190 to 210° C. The pressing pressure is 200 to 500 g / cm in the case of a flat mold. 2 In the case of continuous type, the range is 2 to 6 kg / cm 2 It is preferable that the range is within the range of

[0158] (3) Crystal growth process The crystal growth step is a step of growing crystals of the disperse dye that has dyed the resin (P) after the dyeing step. As described above, in the dyeing step, the disperse dye dyes the resin-attached fabric, specifically the resin (P) applied to the fabric. After the dyeing step, the disperse dye is diffused in the matrix of the resin (P) in a substantially molecular state. The crystal growth step is a step of growing crystals of the disperse dye in the molecular state in the matrix of the resin (P).

[0159] In this way, by growing crystals of the disperse dye in the crystal growth step, the disperse dye that dyed the resin (P) applied to the fabric is crystallized, thereby obtaining the printed fabric of the present invention. As described above, in the printed fabric of the present invention, the disperse dye is crystallized, so the image printed on the fabric has excellent heat resistance. Furthermore, because the printed fabric of the present invention has a simple structure, the texture of the fabric before printing is hardly impaired.

[0160] The method for growing crystals of the disperse dye in the matrix of resin (P) is not particularly limited as long as it is a method that causes crystal growth of the disperse dye. Whether or not the disperse dye has grown crystals in the crystal growth step, i.e., whether or not the disperse dye has crystallized in the resulting printed fabric, can be determined by XRD measurement, as with the printed fabric of the present invention. The degree of crystallization of the disperse dye is not particularly limited as long as the above-mentioned determination conditions are met. The degree of crystallization of the disperse dye can be determined by the size of the crystal particles of the disperse dye. The size of the crystal particles of the disperse dye is preferably within the above-mentioned range.

[0161] A specific example of a method for causing crystal growth of the disperse dye in the matrix of the resin (P) is to wash the fabric (hereinafter also referred to as "printed fabric precursor") after the dyeing step with a washing liquid.

[0162] The washing liquid used for washing the printed fabric precursor is preferably a washing liquid containing water as the main component, and more preferably a washing liquid consisting only of water without any washing components other than water, such as surfactants. That is, water is preferred as the washing liquid. The water may be ion-exchanged water, distilled water, or pure water.

[0163] Specifically, a preferred method for washing the printed fabric precursor is to immerse the printed fabric precursor in a washing liquid, preferably water. The immersion time for immersing the printed fabric precursor in the washing liquid, preferably water, depends on the immersion temperature described below, but is preferably within a range of 30 to 120 seconds, more preferably 30 to 60 seconds.

[0164] By setting the immersion time within the above range, it is possible to carry out crystal growth of the disperse dye in an appropriate range, which is preferable. If the immersion time is 30 seconds or more, crystal growth of the disperse dye is sufficiently carried out, and the heat resistance of the resulting printed image is sufficiently improved. Furthermore, if the immersion time is 120 seconds or less, it is easy to suppress discoloration of the printed image due to excessive crystal growth and dropout of the disperse dye, which causes a decrease in density.

[0165] Furthermore, the immersion temperature when the printed fabric precursor is immersed in a washing liquid, preferably water, is preferably less than 30°C, more preferably in the range of 15 to 25°C, and even more preferably in the range of 20 to 25°C. If the immersion temperature is less than 30°C, it is easy to control the crystal growth of the disperse dye. Furthermore, if the immersion temperature is 15°C or higher, and even more preferably 20°C or higher, production efficiency is improved, which is preferable. The immersion temperature is the temperature of the printed fabric precursor during immersion, and corresponds to the temperature of the washing liquid, preferably water.

[0166] In order to maintain the immersion temperature in the immersion treatment within the above range, it is preferable to keep the temperature of the printed fabric precursor before immersion approximately equal to the temperature of the washing liquid, preferably water, in the immersion treatment. It is also preferable to use a sufficient amount of washing liquid, preferably water, relative to the amount of the printed fabric precursor.

[0167] When the printed fabric precursor is washed as described above to grow crystals of the disperse dye and produce a printed fabric, it is preferable to dry the printed fabric after washing. The drying method is not particularly limited, and heating with hot air, a hot plate, or a heat roller is preferable. From the viewpoint of sufficiently removing the liquid medium in a short time, heated drying is more preferable. The drying temperature is preferably 110°C or less, and more preferably in the range of 70 to 100°C. If the drying temperature is 110°C or less, melting or sublimation of the disperse dye crystals obtained above is suppressed, and the crystalline state can be sufficiently maintained.

[0168] In the textile printing method of the present invention, from the same viewpoint as above, it is preferable not to subject the printed fabric after the crystal growth step to a heat treatment exceeding 110° C. Examples of such a heat treatment include a heat treatment when forming a resin coating layer on the printed fabric after the crystal growth step. [Example]

[0169] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, operations were carried out at room temperature (25°C). Furthermore, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass," respectively.

[0170] [Manufacturing of printed fabrics] Fabrics were printed using disperse dyes and resin (P) by the following method to produce the printed fabrics of the Examples or Comparative Examples shown in Table II. In all examples, cotton broadcloth 40, 100% cotton, was used as the fabric.

[0171] (1) Pretreatment process (1-1) Preparation of pretreatment solution Using the following commercially available products containing resin (P) and ion-exchanged water, aqueous solutions (dispersions) of each resin (P) were prepared to have the compositions shown in Table I, and these were named pretreatment solutions 1 to 5. Specifically, the amount of each component added was adjusted so that the solid content of resin (P) in each pretreatment solution was 20 mass % or 30 mass % (see Table I).

[0172] <Commercially available products> Superflex 300 (Dai-ichi Kogyo Seiyaku Co., Ltd.); Aqueous dispersion of polyurethane resin (resin solid content 30% by mass) SRN170C (Clariant): Aqueous dispersion of polyethylene glycol-polyester (PET) copolymer (resin solids content 70% by mass) SRN260 (Clariant): Aqueous dispersion of polyethylene glycol-polyester (PET) copolymer (resin solid content 60% by mass) PEG6000 (Fujifilm Wako Pure Chemical Industries, Ltd.); polyethylene glycol (resin solid content 100% by mass) PPG (Fujifilm Wako Pure Chemical Industries, Ltd.); Polypropylene glycol (resin solid content 100% by mass) [Table 1]

[0173] (1-2) Pretreatment In each of the Examples and Comparative Examples, the pretreatment liquid shown in Table II was applied to the fabric by the mangle method (dipping method) or the ink-jet method as shown in Table II.

[0174] In the mangle method, the fabric was immersed in a bath filled with a pretreatment liquid (temperature: 20 to 25°C), and then excess pretreatment liquid was squeezed out with a mangle roll so that the pickup rate was 80 mass % (mass ratio of the pretreatment liquid attached to the fabric before immersion). The amount of pretreatment liquid applied to the fabric was 80 g / m 2 (The amount of resin (P) applied after drying is 16 g / m 2 ) was.

[0175] In the inkjet method, an inkjet printer having an inkjet head (Konica Minolta KM1024iMAE) was used to apply a coating amount of 30 g / m 2 (The amount of resin (P) applied after drying is 6 g / m 2 The pretreatment liquid was applied so that

[0176] In each example, after the application of the pretreatment liquid, the fabric was dried at 110°C for 3 minutes to obtain a resin-coated fabric.

[0177] (2) Dyeing process The transfer printing method (sublimation transfer method) was used as the method for dyeing the resin-coated fabric with ink containing disperse dyes.

[0178] (2-1) Preparation of ink Disperbyk-190 (manufactured by BYK Japan, acid value 10 mgKOH / g) as a dispersant and ion-exchanged water were mixed and stirred until uniform, and then CI Disperse Red 60, a sublimation dye, was added as a disperse dye and premixed. The mixture was dispersed until the Z-average particle size measured by dynamic light scattering was within the range of 150 to 200 nm, preparing a dispersion with a disperse dye concentration of 20% by mass.

[0179] The amounts of dispersant, ion-exchanged water, and disperse dye were adjusted so that the disperse dye content was 20% by mass relative to the total mass of the dispersion, and the solid content of the dispersant was 30% by mass relative to the total mass of the disperse dye. Measurement of the Z-average particle size by dynamic light scattering was performed using a sand grinder filled with 0.5 mm zirconia beads at a volume ratio of 50%, using a Zetasizer 1000 manufactured by Malvern ("Zetasizer" is a registered trademark of the company).

[0180] The obtained dispersion liquid was mixed with 30% by mass of glycerin as a solvent, 25% by mass of ethylene glycol as a solvent, 0.1% by mass of Proxel GXL as a preservative, and an appropriate amount of sodium citrate hydrate as a pH adjuster, and then mixed with ion-exchanged water to make a total of 100% by mass.The mixture was then filtered through a 1 μm mesh filter to obtain a magenta dispersion ink.

[0181] (2-2) Applying ink to transfer paper An inkjet printer having an inkjet head (KM1024iMAE manufactured by Konica Minolta, Inc.) was prepared as the image forming apparatus. A4 size adhesive sublimation transfer paper (manufactured by System Graphie) was also prepared as the transfer paper.

[0182] The magenta dispersion ink obtained above was ejected from the nozzles of an inkjet head to form a solid image on transfer paper. Specifically, an image (200 mm x 200 mm in total) including a fine line grid, gradation, and solid areas was formed at 540 dpi in the main scan direction and 720 dpi in the sub-scan direction. dpi represents the number of ink droplets (dots) per 2.54 cm. The ejection frequency was 22.4 kHz. The ink-coated transfer paper was then dried in a dryer at 50 to 80°C for 30 seconds to obtain a transfer paper with an ink layer. In all examples, the transfer paper with the ink layer obtained in this manner was used.

[0183] (2-3) Transferring ink to resin-coated fabric In each example, the transfer paper with the ink layer obtained above was placed on the surface (pre-treated surface) of the resin-coated fabric so that the ink layer was in contact with the surface (pre-treated surface). This was then transferred using a transfer device (heat press) at 200°C for 60 seconds with a pressing pressure of 300 g / cm. 2 Thereby, the ink layer on the transfer paper was transferred onto the resin-coated fabric, and a precursor for printed fabric was obtained.

[0184] (3) Crystal growth process The printed fabric precursor obtained in each example was immersed in a bath filled with ion-exchanged water at 25°C for the time shown in Table II, ranging from 30 to 180 seconds for Examples 1 to 8, and then completely dried at 110°C to obtain a printed fabric. For Comparative Examples 1 to 5, the crystal growth step was not carried out, and the printed fabric precursor obtained above was used as is to form the printed fabric.

[0185] For Comparative Example 6, the printed fabric precursor obtained above was immersed in a bath filled with ion-exchanged water at 25°C for 60 seconds (water washing treatment), taken out, completely dried at 110°C, and further treated by the same mangle method as above using a treatment solution containing 20% ​​by mass of acrylic resin. Thereafter, it was heated and dried at 180°C for 1 minute to obtain a printed fabric with an acrylic resin coating layer.

[0186] Table II shows the type and application method of the pretreatment liquid, the conditions for the crystal growth step, and the presence or absence of a resin coating layer for each example. In this way, the printed fabrics of Examples 1 to 8 and Comparative Examples 1 to 6 were produced, as shown in Table II. Regarding Comparative Example 6, the crystal growth evaluation results below suggest that although the disperse dye was crystallized when the printed fabric precursor was immersed in ion-exchanged water, the disperse dye crystals melted or sublimated during the subsequent heat drying step during the preparation of the resin coating layer, and no crystal peak was observed. In Comparative Example 6, no disperse dye crystals were present in the final printed fabric, and therefore the treatment time for this treatment is listed as "water washing" in the crystal growth step treatment time column in Table II.

[0187] [evaluation] The printed fabrics obtained in each example were evaluated as follows, and the results are shown in Table II. In addition, "Example 7" in "Table II" should be read as "Reference Example."

[0188] (1) Crystal growth evaluation The printed fabric was subjected to XRD measurement under the above conditions, and the presence or absence of a crystalline peak of the disperse dye was confirmed in the obtained XRD spectrum.

[0189] (2) Color development evaluation The image density was measured using a spectrophotometer (manufactured by Konica Minolta) and the K / S value was calculated. The K / S value is an index of surface color density defined by the following formula: Kubelka-Munk equation: K / S=(1-R) 2 / 2S (K: light absorption coefficient, S: light scattering coefficient, R: surface reflectance)

[0190] A larger K / S value means a higher color density, and a smaller K / S value means a lower color density. For the examples, the color density before and after the crystal growth process was compared to calculate the density reduction rate, and the results were evaluated according to the following criteria.

[0191] Concentration reduction rate (%) = (K / S value before crystal growth process - K / S value after crystal growth process) / (K / S value before crystal growth process) × 100

[0192] (Evaluation criteria) 5: Concentration reduction rate is less than 10% 4: Concentration reduction rate is 10% or more but less than 15% 3: Concentration reduction rate is 15% or more but less than 20% 2: Concentration reduction rate is 20% or more but less than 50% 1: Concentration reduction rate is 50% or more

[0193] Since no crystal growth step was performed in Comparative Examples 1 to 5, color development was not evaluated. In Comparative Example 6, the density reduction rate was calculated according to the above formula before and after the water washing treatment and before and after the formation of the resin coating layer, and evaluated according to the same evaluation criteria as above.

[0194] (3) Heat resistance evaluation The printed fabric was combined with unprocessed cotton broadcloth 40 (white fabric) and pressed in a hot press at 200°C for 15 seconds at a pressure of 300g / cm. 2 The pressing operation was carried out five times. The white cloth was replaced each time, and the degree of staining of the white cloth after the fifth pressing operation was visually compared with that of the untreated cotton broadcloth 40 (white cloth) used in the test, and evaluated according to the following criteria.

[0195] (Evaluation criteria) 5: No contamination detected and no change. 4: Contamination is barely noticeable and is at a level that does not pose a problem for practical use. 3: There is slight contamination, but it is at a level that does not cause any problems in practical use. 2: There is contamination, but it is at a level that does not cause any practical problems. 1: Contamination is severe and at a level that is problematic for practical use. (4) Texture evaluation The texture of the resulting printed fabric and raw cotton broadcloth (unprocessed 40cm) was evaluated sensorily by touching with the fingers, and was evaluated based on the following criteria.

[0196] (Evaluation criteria) 5: The original softness of the fabric is maintained, and it is almost the same (as before image formation). 4: The fabric is slightly harder than before image formation, but the texture of the fabric is not impaired and there is no problem in practical use. 3: The fabric is slightly harder than before the image formation, and the texture of the fabric has changed slightly, but this is at a level that does not cause any problems in practical use. 2: The fabric is slightly stiffer than before the image formation, and the texture has changed slightly, but this is not a problem for practical use. 1: The fabric is harder than before image formation, the texture of the fabric is significantly impaired, and it is at a level that is problematic for practical use.

[0197] [Table 2]

[0198] In the printed fabric of the present invention, the disperse dye applied to correspond to the desired image is crystallized in the matrix of the resin (P) applied to the fabric, thereby improving the heat resistance of the image printed on the fabric. Furthermore, in the printed fabric of the present invention, changes in the texture of the fabric before and after printing are suppressed. None of the printed fabrics of the comparative examples achieves both heat resistance and maintenance of texture. The printed fabric of Comparative Example 6 has heat resistance due to the presence of a resin coating layer, but its texture is deteriorated. However, the heat resistance of the printed fabric of Comparative Example 6 is also low because, as mentioned above, the disperse dye is not present in a crystalline state.

Claims

1. A method of printing a fabric to obtain a printed fabric dyed with a disperse dye, the method comprising: adding a dyeable resin to the fabric; dyeing the resin with the disperse dye; and crystallizing the disperse dye, the method comprising the steps of: applying the resin to the fabric; a dyeing step of dyeing the resin applied to the fabric with the disperse dye; and A step of causing crystal growth of the disperse dye after the dyeing step. and the crystal growth step includes a step of washing the fabric after the dyeing step with a washing liquid, The washing is carried out by immersing the fabric after the dyeing step in water, The immersion time is within a range of 30 to 120 seconds, The immersion temperature during the immersion is 15 to 25°C, A textile printing method, characterized in that the printed fabric after the crystal growth step is not subjected to a heat treatment at a temperature exceeding 110°C.

2. 2. The textile printing method according to claim 1, wherein the dyeing is carried out by a sublimation transfer method.

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