Treatment liquid and recording method

Abstract

To provide a recording method which can stably manufacture a recorded matter, while effectively preventing problems of occurrence of transfer failure and migration, and a treatment liquid which can be suitably applied to the recording method.SOLUTION: A treatment liquid is composed of a material containing resin particles, a water-soluble organic solvent, a silicone-based surface active agent and water, and is printed on a transfer medium, wherein a content of the resin particles is 5.0 mass% or more and 20.0 mass% or less, the water-soluble organic solvent contains a substance A and a substance B, a content of the substance A is 5.0 mass% or more and 20.0 mass% or less, a content of the substance B is 0.1 mass% or more and 3.0 mass% or less, and a content of an organic solvent having a boiling point of higher than 230°C is 10.0 mass% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a treatment liquid and a recording method. [Background technology]

[0002] A transfer printing method is known in which a transfer sheet, which is a transfer medium on which an image has been formed, is superimposed on a receiving medium such as fabric, and the image is transferred to the receiving medium by applying heat and pressure. In such a method, an inkjet method is often used when forming an image on the transfer sheet, because it is advantageous in forming a fine image with high on-demand performance.

[0003] In the transfer printing method described above, an image is generally formed on a transfer sheet having a release layer and a hot melt layer formed on the entire surface of a substrate, and then this transfer sheet is heated and pressed onto a medium to be transferred.

[0004] Patent Document 1 discloses a method for manufacturing a transfer medium, which includes a colored layer forming step of ejecting ink from an inkjet head toward a substrate to form a colored layer on the substrate, and an adhesive layer forming step of ejecting an adhesive liquid, which is an aqueous liquid containing an emulsion-type polyester resin with a glass transition temperature of 10° C. or more and 70° C. or less, from the inkjet head toward the colored layer to form an adhesive layer on the colored layer. The document describes that the above-described configuration provides excellent ejection stability when the adhesive liquid is ejected from the inkjet head, enables the colored layer pattern to be obtained with high resolution, and provides a method for manufacturing a transfer medium that is excellent in transferability, adhesion after transfer, and blocking resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-059973 Summary of the Invention [Problem to be solved by the invention]

[0006] Patent Document 1 discloses the use of plastic or metal as a transfer medium, but does not disclose the use of an absorbent transfer medium such as fabric. When the transfer medium described in Patent Document 1 is applied to an absorbent transfer medium such as fabric for transfer, migration problems occur. In other words, if the transfer medium is dyed with a dye, the dye moves from its original location on the transfer medium to another location. Therefore, there is a need to provide a recording method that can effectively prevent the occurrence of migration problems, and a processing liquid that can be used in the recording method. [Means for solving the problem]

[0007] The present invention has been made to solve the above-mentioned problems, and can be realized as the following application examples.

[0008] The treatment liquid according to the application example of the present invention is made of a material containing resin particles, a water-soluble organic solvent, a silicone surfactant, and water, and is printed on a transfer medium. The content of the resin particles is 5.0% by mass or more and 20.0% by mass or less, the water-soluble organic solvent contains a substance A and a substance B, The content of the substance A is 5.0% by mass or more and 20.0% by mass or less, The content of the substance B is 0.1% by mass or more and 3.0% by mass or less, The content of organic solvents with a boiling point exceeding 230°C is 10.0 mass% or less. (wherein the substance A is at least one compound selected from diols having a solubility in water at 25°C of more than 1.00 [g / 100 g HO] and a boiling point of 230°C or less, and the substance B is at least one compound selected from a group of compounds having a solubility in water at 25°C of 0.10 [g / 100 g HO] or more and 1.00 [g / 100 g HO] or less.)

[0009] A recording method according to an application example of the present invention includes a first layer forming step of ejecting an image forming ink from an inkjet head onto a transfer medium having a release layer to form a first layer; a second layer forming step of ejecting a treatment liquid from an inkjet head to form a second layer so as to overlap the first layer; a thermal transfer step of thermally transferring the first layer and the second layer to an absorbent medium by heating the surface of the transfer medium on which the first layer and the second layer are formed while the surface is opposed to the absorbent medium, The treatment liquid is composed of a material containing resin particles, a water-soluble organic solvent, a silicone surfactant, and water, the content of the resin particles being 5.0% by mass or more and 20.0% by mass or less, the water-soluble organic solvent containing substance A and substance B, the content of substance A being 5.0% by mass or more and 20.0% by mass or less, the content of substance B being 0.1% by mass or more and 3.0% by mass or less, and the content of organic solvents having a boiling point above 230°C being 10.0% by mass or less. (wherein the substance A is at least one compound selected from diols having a solubility in water at 25°C of more than 1.00 [g / 100 g HO] and a boiling point of 230°C or less, and the substance B is at least one compound selected from a group of compounds having a solubility in water at 25°C of 0.10 [g / 100 g HO] or more and 1.00 [g / 100 g HO] or less.) [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a process diagram showing a preferred embodiment of the recording method of the present invention. [Figure 2] FIG. 2 is a table showing the compositions of the image-forming inks of Preparation Examples 1 to 3. [Figure 3] FIG. 3 is a table showing the compositions of the treatment liquids of Examples A1 to A12. [Figure 4] FIG. 4 is a table showing the compositions of the treatment liquids of Examples A13 to A16 and Comparative Examples A1 to A7. [Figure 5]FIG. 5 is a table summarizing the conditions of the recording methods of Examples B1 to B12. [Figure 6] FIG. 6 is a table summarizing the conditions of the recording methods of Examples B13 to B16 and Comparative Examples B1 to B7. [Figure 7] FIG. 7 is a table summarizing the evaluation results of Examples A1 to A12 and Examples B1 to B12. [Figure 8] FIG. 8 is a table summarizing the evaluation results of Examples A13 to B16, Examples B13 to B16, Comparative Examples A1 to A7, and Comparative Examples B1 to B7. DETAILED DESCRIPTION OF THE INVENTION

[0011] Preferred embodiments of the present invention will be described in detail below. The embodiments described below are examples of the present invention. The present invention is not limited to the following embodiments, and includes various modifications that are implemented within the scope of the present invention. Note that not all of the configurations described below are necessarily essential configurations of the present invention.

[0012] [1] Processing solution First, the processing liquid of the present invention will be described.

[0013] The treatment liquid of the present invention is a treatment liquid to be printed on a transfer medium, and is composed of a material containing resin particles, a water-soluble organic solvent, a silicone surfactant, and water. The content of the resin particles in the treatment liquid of the present invention is from 5.0% to 20.0% by mass, the water-soluble organic solvent contains substance A and substance B, the content of substance A is from 5.0% to 20.0% by mass, the content of substance B is from 0.1% to 3.0% by mass, and the content of the organic solvent having a boiling point above 230°C is 10.0% by mass or less. However, the substance A is at least one compound selected from diols having a solubility in water at 25°C of more than 1.00 [g / 100 g H2O] and a boiling point of 230°C or less, and the substance B is at least one compound selected from a group of compounds having a solubility in water at 25°C of 0.10 [g / 100 g H2O] or more and 1.00 [g / 100 g H2O] or less.

[0014] This makes it possible to provide a treatment liquid that has excellent ejection stability when used in an inkjet method, and that has excellent transferability and can effectively prevent the occurrence of migration problems even when applied to an absorbent transfer medium. In other words, when a recording portion made of the treatment liquid printed on a transfer medium is transferred to an absorbent transfer medium, it is possible to effectively prevent the occurrence of transfer defects and migration problems.

[0015] On the other hand, if the above conditions are not met, satisfactory results will not be obtained. For example, if the water-soluble organic solvent contains substance A but does not contain substance B, migration problems are more likely to occur when a recording area made of a processing liquid printed on a transfer medium is transferred to an absorbent transfer medium.

[0016] Furthermore, even if the water-soluble organic solvent contains substance B, if substance A is not contained, the ejection stability of the treatment liquid when ink-jet printing is performed will be significantly reduced.

[0017] Furthermore, even if the water-soluble organic solvent contains substance A and substance B, if the content of substance A is less than the lower limit, the ejection stability of the treatment liquid when ink-jet printed is not sufficiently excellent.

[0018] Furthermore, even if the water-soluble organic solvent contains substance A and substance B, if the content of substance A exceeds the upper limit, migration problems become significantly more likely to occur when a recording area made of the treatment liquid printed on a transfer medium is transferred to an absorbent transfer medium.

[0019] Furthermore, even if the water-soluble organic solvent contains substance A and substance B, if the content of substance B is less than the lower limit, the ejection stability of the treatment liquid when used in an inkjet method cannot be sufficiently excellent.

[0020] Furthermore, even if the water-soluble organic solvent contains substance A and substance B, if the content of substance B exceeds the upper limit, the storage stability of the treatment liquid and the ejection stability by the inkjet method will be significantly reduced.

[0021] Furthermore, if the content of organic solvents with a boiling point above 230°C is too high, migration problems become significantly more likely to occur when a recording area made of the treatment liquid printed on a transfer medium is transferred to an absorbent transfer medium.

[0022] Furthermore, if the treatment liquid does not contain a silicone surfactant, the storage stability of the treatment liquid and the ejection stability when using an inkjet method will be significantly reduced.

[0023] In this specification, the boiling point refers to the boiling point under 1 atmosphere unless otherwise specified.

[0024] [1-1] Resin particles The treatment liquid of the present invention contains resin particles.

[0025] The resin particles contained in the treatment liquid of the present invention are usually water-based resin particles that have excellent dispersibility in liquids containing water as the main component.

[0026] This allows the recording portion formed by the recording method described later in detail to have excellent adhesion to the transfer medium, and the durability of the produced recorded matter to be excellent.

[0027] In particular, the treatment liquid of the present invention contains a resin in the form of particles. This makes it possible to improve the ejection stability of the treatment liquid when used in an inkjet method, and to more stably produce recorded matter, which will be described later. In the recording method, which will be described later in detail, it is possible to effectively prevent liquid components from unintentionally remaining in the recording section.

[0028] The average particle size of the resin particles in the treatment liquid is preferably 30 nm or more and 3 μm or less, more preferably 50 nm or more and 1 μm or less, and even more preferably 60 nm or more and 300 nm or less. This makes the above-mentioned effects more pronounced.

[0029] In this specification, the average particle size refers to the average particle size on a volume basis, and can be determined, for example, by adding a sample to methanol, dispersing the dispersion for 3 minutes using an ultrasonic disperser, and measuring the dispersion using a Coulter Counter particle size distribution analyzer (TA-II model, manufactured by COULTER ELECTRONICS INS) with a 50 μm aperture.

[0030] Examples of resin materials that make up the resin particles include polyurethane resin, polyester resin, polyvinyl chloride, styrene-acrylic resin, acrylic resin, etc., and one or more selected from these can be used in combination, but it is preferable that the resin particles be made up of a material that contains at least one of a urethane resin and a polyester resin.

[0031] This allows for improved transferability of the recorded portion formed by the recording method described in detail below to the transfer medium and durability of the produced recorded matter. In particular, when the resin particles are made of a material containing polyester resin, the following effects are achieved. Conventionally, when the transfer medium is a polyester fabric, the transferability of the recorded portion from the transfer medium to the transfer medium and the durability of the recorded matter tend to be poor. However, the present invention can effectively prevent such problems. In other words, when the resin particles are made of a material containing polyester resin, even when a polyester fabric transfer medium is used as the transfer medium, the transferability of the recorded portion from the transfer medium to the transfer medium and the durability of the recorded matter, such as washing fastness, can be sufficiently improved.

[0032] The glass transition temperature of the resin material constituting the resin particles is preferably -20°C or higher and 50°C or lower, more preferably -10°C or higher and 45°C or lower, and even more preferably 0°C or higher and 40°C or lower.

[0033] This makes it possible to improve the texture and durability such as washing fastness of the recorded matter produced by the recording method described in detail later.

[0034] The melting point of the resin material constituting the resin particles is preferably 80°C or higher and 140°C or lower, more preferably 85°C or higher and 130°C or lower, and even more preferably 90°C or higher and 120°C or lower.

[0035] This makes it possible to improve the texture and durability such as washing fastness of the recorded matter produced by the recording method described in detail later.

[0036] The content of resin particles in the treatment liquid of the present invention may be from 5.0% to 20.0% by mass, preferably from 7.0% to 18.0% by mass, and more preferably from 8.0% to 17.0% by mass. This allows the effects of the present invention to be more pronounced.

[0037] [1-2] Water-soluble organic solvents The treatment liquid of the present invention contains a water-soluble organic solvent.

[0038] This allows the viscosity and surface tension of the treatment liquid to be suitably adjusted. In addition, for example, the moisturizing properties of the treatment liquid are improved, which effectively prevents the solid content of the treatment liquid from unintentionally precipitating due to drying in an inkjet head or the like, improves clogging recovery, and improves the ejection stability of the treatment liquid.

[0039] In particular, the treatment liquid of the present invention contains, as the water-soluble organic solvent, substance A and substance B as described below in predetermined contents.

[0040] That is, the water-soluble organic solvent contains, as substance A, at least one compound selected from diols having a solubility in water at 25°C of more than 1.00 [g / 100 g HO] and a boiling point of 230°C or less, and contains, as substance B, at least one compound selected from a group of compounds having a solubility in water at 25°C of 0.10 [g / 100 g HO] or more and 1.00 [g / 100 g HO] or less. The content of substance A in the treatment liquid of the present invention is 5.0% by mass or more and 20.0% by mass or less, the content of substance B is 0.1% by mass or more and 3.0% by mass or less, and the content of organic solvents having a boiling point of more than 230°C is 10.0% by mass or less.

[0041] [1-2-1]Substance A Substance A is at least one compound selected from diols having a solubility in water at 25° C. of more than 1.00 [g / 100 gH2O] and a boiling point of not more than 230° C. Since substance A tends to have a high affinity for water, it is possible to ensure the ejection stability of the treatment liquid even when the treatment liquid contains substance B, which will be described later.

[0042] The solubility of substance A in water at 25°C may be more than 1.00 [g / 100gH2O], preferably 5.0 [g / 100gH2O] or more, and more preferably 10.0 [g / 100gH2O] or more. In particular, substance A is preferably compatible with water at 25°C in any proportion. This allows the effects of the present invention to be more pronounced.

[0043] The boiling point of substance A may be 230°C or lower, but is preferably 170°C or higher and 225°C or lower. This allows the effects of the present invention to be more pronounced.

[0044] Examples of compounds that satisfy the above-mentioned conditions of solubility in water and boiling point include propylene glycol (miscible, boiling point: 188°C), 1,3-propanediol (miscible, boiling point: 214°C), 1,2-butanediol (miscible, boiling point: 194°C), 1,3-butanediol (miscible, boiling point: 207°C), and 1,2-hexanediol (miscible, boiling point: 224°C). One or a combination of two or more selected from these can be used as substance A, but substance A is preferably at least one of propylene glycol and 1,2-hexanediol, and more preferably contains both propylene glycol and 1,2-hexanediol. This allows the effects of the present invention to be more pronounced.

[0045] When the substance A constituting the treatment liquid of the present invention contains both propylene glycol and 1,2-hexanediol, it is preferable that the content of propylene glycol in the treatment liquid of the present invention is X PG [mass%], the content of 1,2-hexanediol in the treatment liquid is X HD When expressed as [mass %], 0.10≦X HD / X PG It is preferable to satisfy the relationship of 0.15≦X HD / XPG It is more preferable that the relationship satisfies 0.20≦X HD / X PG It is more preferable that the relationship be ≦0.40. This allows the effects of the present invention to be more pronounced.

[0046] The content of substance A in the treatment liquid of the present invention may be 5.0% by mass or more and 20.0% by mass or less, preferably 6.0% by mass or more and 17.0% by mass or less, and more preferably 7.0% by mass or more and 15.0% by mass or less. This allows the effects of the present invention to be more pronounced.

[0047] [1-2-2] Substance B The substance B is at least one compound selected from a group of compounds having a solubility in water at 25°C of 0.10 [g / 100 g HO] or more and 1.00 [g / 100 g HO] or less. Because substance B tends to have low affinity with water, it has a high affinity with low-absorption or non-absorption transfer media, improving the wetting and spreading of a treatment liquid containing it onto the transfer medium. Therefore, by including substance B in the treatment liquid, the treatment liquid dries well, effectively preventing the remaining liquid components capable of dissolving the dye present on the transfer medium during the thermal transfer process described below.

[0048] The solubility of substance B in water at 25°C may be from 0.10 [g / 100g H2O] to 1.00 [g / 100g H2O], preferably from 0.12 [g / 100g H2O] to 0.98 [g / 100g H2O], more preferably from 0.15 [g / 100g H2O] to 0.95 [g / 100g H2O], and even more preferably from 0.60 [g / 100g H2O] to 0.93 [g / 100g H2O]. This allows the effects of the present invention to be more pronounced.

[0049] The boiling point of substance B is preferably 210°C or higher and 330°C or lower, more preferably 240°C or higher and 310°C or lower, and even more preferably 250°C or higher and 270°C or lower. This allows the effects of the present invention to be more pronounced.

[0050] Examples of compounds that satisfy the above-mentioned conditions of solubility in water and boiling point include 2,2'-butylethyl-1,3-propanediol, 1,2-octanediol, ethylhexylglycerin, diethylene glycol monoethylhexyl ether, N-octyl-2-pyrrolidone, etc. One or a combination of two or more selected from these can be used as substance B, but it is preferable that substance B is 2,2'-butylethyl-1,3-propanediol. This allows the effects of the present invention to be more pronounced.

[0051] In particular, when substance A contains both propylene glycol and 1,2-hexanediol and substance B is 2,2'-butylethyl-1,3-propanediol, these components act synergistically, and the effects of the present invention described above are even more pronounced.

[0052] The content of substance B in the treatment liquid of the present invention may be from 0.1% to 3.0% by mass, preferably from 0.2% to 2.0% by mass, and more preferably from 0.3% to 1.2% by mass. This allows the effects of the present invention to be more pronounced.

[0053] The content of substance A in the processing solution of the present invention is X A [mass%], the content of substance B in the treatment liquid is X B When expressed as [mass %], 0.01≦X B / X A It is preferable to satisfy the relationship of 0.02≦X B / X A It is more preferable that the relationship of 0.03≦XB / X A It is more preferable that the relationship be ≦0.20. This allows the effects of the present invention to be more pronounced.

[0054] [1-2-3] Other solvent components The water-soluble organic solvent constituting the treatment liquid of the present invention may contain the above-mentioned substance A and substance B in a predetermined content range, but may also contain components other than substance A and substance B. Hereinafter, such components will also be referred to as "other solvent components."

[0055] The solubility of the other solvent components in water at 25°C is preferably 0.05 [g / 100gH2O] or more, more preferably 0.10 [g / 100gH2O] or more, and even more preferably 0.15 [g / 100gH2O] or more.

[0056] The content of other solvent components in the treatment liquid of the present invention is preferably 2.5% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less.

[0057] [1-2-4] Other conditions The content of the water-soluble organic solvent in the treatment liquid of the present invention is preferably 5.1% by mass or more and 25.0% by mass or less, more preferably 6.2% by mass or more and 20.0% by mass or less, and even more preferably 7.2% by mass or more and 17.0% by mass or less.

[0058] This makes it possible to more suitably adjust the viscosity and surface tension of the treatment liquid, and also improves the moisturizing properties of the treatment liquid, more effectively preventing unintended precipitation of solids in the treatment liquid due to drying in an inkjet head or the like, improving recovery from clogging, and improving the ejection stability of the treatment liquid.

[0059] The content of organic solvents having a boiling point of more than 230° C. in the treatment liquid of the present invention is 10.0 mass % or less.

[0060] In this way, by keeping the content of the high-boiling organic solvent at or below the predetermined value, the above-mentioned migration problem can be more effectively prevented.

[0061] As described above, the content of organic solvents having a boiling point of more than 230°C in the treatment liquid of the present invention may be 10.0% by mass or less, preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.2% by mass or less. This allows the effects of the present invention to be more pronounced.

[0062] [1-3] Silicone surfactants The treatment liquid of the present invention contains a silicone surfactant, which is a component that can effectively reduce the surface tension of the treatment liquid containing substance B.

[0063] Examples of silicone surfactants include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348, BYK-349, and BYK-3455 manufactured by BYK Japan; Silface SAG503A, SAG002, SAG005, and SAG014 manufactured by Nissin Chemical Industry Co., Ltd.; and KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, and KF-6012 manufactured by Shin-Etsu Chemical Co., Ltd., and these may be used alone or in combination of two or more.

[0064] The content of the silicone surfactant in the treatment liquid of the present invention is preferably 0.02% by mass or more and 1.50% by mass or less, more preferably 0.05% by mass or more and 1.00% by mass or less, and even more preferably 0.10% by mass or more and 0.70% by mass or less.

[0065] This makes it possible to improve the ejection stability of the treatment liquid when using an inkjet method.

[0066] [1-4]Water The treatment liquid of the present invention contains water. The treatment liquid of the present invention is usually a water-based ink composition containing water as a main component.

[0067] In the treatment liquid of the present invention, water is a component that functions as, for example, a dispersion medium for dispersing resin particles.

[0068] The water content in the treatment liquid of the present invention is preferably 50.0% by mass or more and 85.0% by mass or less, more preferably 55.0% by mass or more and 80.0% by mass or less, and even more preferably 60.0% by mass or more and 75.0% by mass or less.

[0069] [1-5] Other ingredients The treatment liquid of the present invention may contain components other than those described above. Hereinafter, in this section, such components will also be referred to as "other components."

[0070] Examples of other components include surfactants other than silicone surfactants; resin materials contained in a dissolved state; chelating agents; preservatives; mildew inhibitors; rust inhibitors; flame retardants; various dispersants; pH adjusters such as triethanolamine; antioxidants; ultraviolet absorbers; oxygen absorbers; dissolution aids; and penetrating agents.

[0071] Examples of surfactants other than silicone surfactants include various nonionic surfactants other than silicone surfactants, cationic surfactants, anionic surfactants, and the like.

[0072] Examples of nonionic surfactants other than silicone surfactants include acetylene glycol surfactants.

[0073] Examples of acetylene glycol surfactants include Surfynol 82, 465, 485, 2502, Olfine E1004, E1010, E1020, PD-002W, PD-004, EXP4001, EXP4002, EXP4123, and EXP4300, manufactured by Nissin Chemical Industry Co., Ltd.; and Acetylenol E00, E103T, E40, E60, E100, and E200, manufactured by Kawaken Fine Chemicals Co., Ltd. ("Surfynol" and "Olfine" are registered trademarks).

[0074] However, it is preferable that the treatment liquid of the present invention does not contain a fluorine-based surfactant. The treatment liquid of the present invention preferably does not contain a coloring material.

[0075] The content of other components in the treatment liquid of the present invention is preferably 6.0% by mass or less, and more preferably 5.0% by mass or less. The lower limit of the content of other components is 0% by mass.

[0076] [1-6] Other conditions The viscosity of the treatment liquid of the present invention at 25° C. is preferably from 2 mPa·s to 10 mPa·s, and more preferably from 3 mPa·s to 8 mPa·s.

[0077] This makes it more difficult for nozzles of the inkjet head to become clogged, further improving the ejection stability of the treatment liquid. Furthermore, even if the nozzles do become clogged, the nozzles can be more easily recovered by capping them.

[0078] The surface tension of the treatment liquid of the present invention at 25°C is not particularly limited, but is preferably 20 mN / m or more and 60 mN / m or less, more preferably 25 mN / m or more and 50 mN / m or less, and even more preferably 27 mN / m or more and 40 mN / m or less.

[0079] This makes it more difficult for nozzles of the inkjet head to become clogged, further improving the ejection stability of the treatment liquid. Furthermore, even if the nozzles do become clogged, the nozzles can be more easily recovered by capping them.

[0080] [2] Recording method Next, the recording method of the present invention will be described.

[0081] FIG. 1 is a process diagram showing a preferred embodiment of the recording method of the present invention. The recording method of the present invention comprises a first layer forming step (1a) of ejecting an image forming ink 2' from an inkjet head 50 onto a transfer medium 1 having a release layer 12 to form a first layer 2, a second layer forming step (1b) of ejecting a treatment liquid 3' from the inkjet head 50' to form a second layer 3 so as to overlap the first layer 2, and a thermal transfer step (1d) of thermally transferring the first layer 2 and the second layer 3 onto an absorbent transfer medium 5 by heating the surface of the transfer medium 1 on which the first layer 2 and second layer 3 have been formed while facing the transfer medium 5. The treatment liquid 3' used satisfies the conditions described in [1] above. Specifically, the treatment liquid 3' is composed of a material containing resin particles, a water-soluble organic solvent, a silicone surfactant, and water, the resin particle content being 5.0% to 20.0% by mass, the water-soluble organic solvent containing substance A and substance B, the substance A content being 5.0% to 20.0% by mass, the substance B content being 0.1% to 3.0% by mass, and the organic solvent content having a boiling point above 230°C being 10.0% by mass or less, where substance A is at least one compound selected from diols having a solubility in water at 25°C of more than 1.00 [g / 100 g HO] and a boiling point of 230°C or less, and substance B is at least one compound selected from a group of compounds having a solubility in water at 25°C of 0.10 to 1.00 [g / 100 g HO].

[0082] This makes it possible to provide a recording method that can stably produce recorded matter while effectively preventing the occurrence of problems such as poor transfer and migration.

[0083] In the present invention, the absorbent medium refers to a medium that has the property of absorbing a liquid, and quantitatively, it is a medium that has the property of absorbing a liquid within 30 msec from the start of contact in the Bristow method. 1 / 2 Water absorption up to 10mL / m 2 Non-absorbent or low-absorbent media refers to media that do not absorb liquid at all or absorb very little, and quantitatively, in the Bristow method, the media absorbs liquid within 30 msec from the start of contact. 1 / 2 Water absorption up to 10mL / m 2 This refers to the medium described below. The Bristow method is the most widely used method for measuring liquid absorption in a short period of time, and is also adopted by the Japan Pulp and Paper Technical Association (JAPAN TAPPI). Details of the test method are described in Standard No. 51 "Paper and paperboard - Liquid absorbency test method - Bristow method" of the "JAPAN TAPPI Paper and Pulp Test Method 2000 Edition."

[0084] [2-1] First layer formation process In the first layer forming step, an image forming ink 2' is ejected from an inkjet head 50 onto a transfer medium 1 having a release layer 12 to form a first layer 2 (1a).

[0085] [2-1-1] Transfer medium The transfer medium 1 may be any medium having a release layer 12, but in this embodiment, it has a substrate 11 and a release layer 12. This makes the transfer medium 1 easier to handle.

[0086] Although there are no particular limitations on the shape of the transfer medium 1, a sheet-like one is preferably used, which allows the first layer 2 and the second layer 3 to be more suitably formed by the inkjet method.

[0087] Examples of materials that can be used for the substrate 11 include paper, plastic materials, and metal materials. Of these, plastic materials are preferred. Because plastic materials are non-absorbent, the materials that make up the first layer 2 and the second layer 3 are absorbed into the substrate 11, which can effectively prevent the materials from unintentionally remaining after the thermal transfer process.

[0088] Examples of plastic materials that can be used to form the substrate 11 include polyesters such as polyethylene terephthalate, and polyolefins such as polyethylene and polypropylene.

[0089] The substrate 11 may be in any shape, but is preferably in the form of a sheet. When the substrate 11 is in the form of a sheet, the thickness of the substrate 11 is preferably 50 μm or more and 200 μm or less.

[0090] The release layer 12 is a layer having releasability. By including the release layer 12 in the transfer medium 1, it is possible to suitably prevent the constituent materials of the first layer 2 and the second layer 3 from unintentionally remaining on the transfer medium 1 after the thermal transfer step.

[0091] The release layer 12 is preferably non-absorbent or has low absorbency. This makes it possible to more suitably prevent the constituent materials of the first layer 2 and the second layer 3 from being absorbed into the release layer 12 and remaining unintentionally after the thermal transfer step.

[0092] Examples of materials constituting the release layer 12 include polyethylene wax-based release agents, silicone-based release agents, and fluorine-based release agents.

[0093] The thickness of the release layer 12 is not particularly limited, but is preferably 5 μm or more and 80 μm or less, and more preferably 10 μm or more and 50 μm or less.

[0094] In particular, it is preferable that the transfer medium 1 has an ink-receiving layer containing an inorganic oxide as the release layer 12. This makes it possible to form a higher definition image.

[0095] [2-1-2] Image forming ink The image forming ink 2 ′ is ink used to form an image to be transferred onto the transfer receiving medium 5 . The image forming ink 2' contains a coloring material and water.

[0096] [2-1-2-1] Coloring materials The coloring materials contained in the image-forming ink 2' include various inorganic pigments, organic pigments, and various dyes, and one or more selected from these can be used in combination, but pigments are particularly preferred.

[0097] Examples of inorganic pigments include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

[0098] Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates such as basic dye chelates and acid dye chelates; dye lakes such as basic dye lakes and acid dye lakes; nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.

[0099] More specifically, examples of carbon black used as black pigments include No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. (all manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (all manufactured by Columbia Carbon Co.), Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (all manufactured by Cabot Corporation), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (all manufactured by Evonik), etc.

[0100] Examples of white pigments include CI Pigment White 6, 18, and 21.

[0101] Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, and 180.

[0102] Examples of reddish purple pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48(Ca), 48(Mn), 57(Ca), 57:1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168, 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, and 245, and CI Pigment Violet. Examples include 19, 23, 32, 33, 36, 38, 43, and 50.

[0103] Examples of indigo purple pigments include CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, and 66, and CI Vat Blue 4 and 60.

[0104] Examples of pigments other than those mentioned above include CI Pigment Green 7 and 10, CI Pigment Brown 3, 5, 25 and 26, and CI Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43 and 63.

[0105] The image forming ink 2' may contain a self-dispersing pigment as a coloring material. Self-dispersing pigments have hydrophilic groups on their surface, and examples of such hydrophilic groups include -OM, -COOM, -CO-, -SO3M, -SO2M, -SON2NH2, -RSO2M, -PO3HM, -PO3M2, -SON2NHCOR, -NH3, and -NR3. In the formulas, M represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium, and R represents an alkyl group having from 1 to 12 carbon atoms or a naphthyl group which may have a substituent. A phenyl group, for example, may be present between the pigment surface and the hydrophilic group.

[0106] Self-dispersing pigments can be produced by, for example, subjecting a pigment to a physical or chemical treatment to bond hydrophilic groups to the pigment surface. Examples of such physical treatments include vacuum plasma treatment. Examples of chemical treatments include wet oxidation, in which the pigment is oxidized in water with an oxidizing agent.

[0107] Furthermore, as the self-dispersing pigment, for example, a self-dispersing pigment that has been surface-treated by oxidation treatment with hypohalous acid and / or a hypohalite, oxidation treatment with ozone, or oxidation treatment with persulfuric acid and / or a persulfate is preferred in terms of high color development. Furthermore, as the self-dispersing pigment, commercially available products can also be used, and preferred examples include Microjet CW1 (manufactured by Orient Chemical Industries Co., Ltd.), CAB-O-JET250C, CAB-O-JET260M, CAB-O-JET270Y, CAB-O-JET444MP (all manufactured by Cabot Corporation), etc.

[0108] The content of the colorant in the image-forming ink 2' is not particularly limited, but is preferably 1.0% by mass or more and 25.0% by mass or less, more preferably 2.0% by mass or more and 20.0% by mass or less, and even more preferably 5.0% by mass or more and 15.0% by mass or less.

[0109] This makes it easier to ensure sufficient color density in the recording area 4 formed using the image-forming ink 2', thereby improving the color development on the transfer medium 5, and also improving the storage stability of the image-forming ink 2', the ejection stability by the inkjet method, and the ability to recover from clogging in the inkjet head.

[0110] [2-1-2-2]Water The image-forming ink 2' contains water.

[0111] Water is a component that functions as a dispersion medium for dispersing coloring materials and a solvent for dissolving coloring materials in the image-forming ink 2'.

[0112] The water content in the image-forming ink 2' is preferably 50.0% by mass or more and 75.0% by mass or less, more preferably 52.0% by mass or more and 70.0% by mass or less, and even more preferably 54.0% by mass or more and 65.0% by mass or less.

[0113] [2-1-2-3] Organic Solvent The image-forming ink 2' may contain an organic solvent.

[0114] This allows the viscosity and surface tension of the image-forming ink 2' to be suitably adjusted. Furthermore, for example, the image-forming ink 2' has excellent moisture retention, which more effectively prevents the solid content of the image-forming ink 2' from unintentionally precipitating due to drying in an inkjet head or the like, improves clogging recovery, and improves the ejection stability of the image-forming ink 2'.

[0115] As the organic solvent, a water-soluble organic solvent is preferably used. As such a water-soluble organic solvent, an organic solvent having a solubility in water at 25° C. of 10 g / 100 g water or more can be suitably used.

[0116] The organic solvents contained in the image-forming ink 2', particularly the water-soluble organic solvents, include, for example, polyol compounds, glycol ethers, cyclic amide compounds, etc., and one or more selected from these can be used in combination.

[0117] Examples of polyol compounds include polyol compounds having 2 to 6 carbon atoms in the molecule and optionally having one ether bond in the molecule, preferably diol compounds. Specific examples include 1,2-pentanediol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, 1,2-hexanediol, 1,2-heptanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, Examples of glycols include 2,3-butanediol, 2-methyl-3-phenoxy-1,2-propanediol, 3-(3-methylphenoxy)-1,2-propanediol, 3-hexyloxy-1,2-propanediol, 2-hydroxymethyl-2-phenoxymethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, and 3-methyl-1,5-pentanediol.

[0118] Examples of glycol ethers include monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. Examples of the monoalkyl ethers include triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triethylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

[0119] Examples of cyclic amide compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, 2-piperidone (δ-valerolactam), and N-cyclohexyl-2-pyrrolidone.

[0120] The content of the organic solvent in the image-forming ink 2' is preferably 5.0% by mass or more and 35.0% by mass or less, more preferably 10.0% by mass or more and 30.0% by mass or less, and even more preferably 15.0% by mass or more and 25.0% by mass or less.

[0121] This allows the viscosity and surface tension of the image-forming ink 2' to be more suitably adjusted. Also, the image-forming ink 2' has better moisture retention, which more effectively prevents the solid content of the image-forming ink 2' from unintentionally precipitating due to drying in an inkjet head or the like, improves clogging recovery, and improves the ejection stability of the image-forming ink 2'.

[0122] [2-1-2-4] Resin The image forming ink 2' may contain a resin.

[0123] This can improve, for example, the adhesion of the recording portion 4 containing a coloring material to the transfer medium 5. Furthermore, when the image forming ink 2' contains a pigment, the dispersion stability of the pigment in the image forming ink 2' can be improved.

[0124] However, the resin content in the image forming ink 2' is preferably 15.0% by mass or less, more preferably 2.0% by mass or more and 13.0% by mass or less, even more preferably 4.0% by mass or more and 12.0% by mass or less, and most preferably 7.0% by mass or more and 11.0% by mass or less.

[0125] This improves the ejection stability of the image-forming ink 2' using the inkjet method, the manufacturing stability of the recorded matter 100, and the texture of the recorded matter 100, while also improving the dispersion stability of the pigment in the image-forming ink 2' and the adhesion of the recording unit 4 to the transfer medium 5.

[0126] When the image-forming ink 2' contains a resin, the form of the resin in the image-forming ink 2' is not particularly limited. For example, the resin may be contained in the image-forming ink 2' in a dispersed state or in a dissolved state, but is preferably contained in a dispersed state.

[0127] This makes it possible to improve the ejection stability of the image forming ink 2' by the ink jet method, and to produce the recorded matter 100 more stably.

[0128] When the resin is contained in a dispersed state in the image forming ink 2', the average particle size of the resin is preferably 30 nm or more and 3 μm or less, more preferably 50 nm or more and 1 μm or less, and even more preferably 60 nm or more and 300 nm or less. This makes the above-mentioned effects more pronounced.

[0129] Examples of resins contained in the image-forming ink 2' include polyurethane, polyester, styrene-acrylic resin, acrylic resin, polyvinyl chloride, etc., and one or more selected from these may be used in combination. Among these, polyurethane is preferred. This makes the above-mentioned effects more pronounced.

[0130] The glass transition temperature of the resin contained in the image-forming ink 2' is preferably -40°C or higher and 0°C or lower, more preferably -35°C or higher and -5°C or lower, and even more preferably -30°C or higher and -10°C or lower.

[0131] This makes it possible to improve the texture and durability of the produced recorded matter 100, such as washing fastness.

[0132] When the resin content in the image-forming ink 2′ is XR [mass %] and the colorant content is XP [mass %], it is preferable to satisfy the relationship 0.2≦XR / XP≦1.8, it is more preferable to satisfy the relationship 0.6≦XR / XP≦1.5, and it is even more preferable to satisfy the relationship 0.8≦XR / XP≦1.2.

[0133] This makes it easier to ensure sufficient color density in the recording portion 4 formed using the image-forming ink 2', and improves the color development on the transfer medium, as well as improving the storage stability of the image-forming ink 2', the ejection stability by the inkjet method, and the ability to recover from clogging in the inkjet head.In addition, the texture of the recorded product 100 and the adhesion of the recording portion 4 to the transfer medium 5 can be improved.

[0134] [2-1-2-5] Surfactants The image-forming ink 2' may contain a surfactant.

[0135] As the surfactant, various surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants can be used.

[0136] When the image-forming ink 2' contains a surfactant, the content of the surfactant in the image-forming ink 2' is preferably 0.02% by mass or more and 1.50% by mass or less, more preferably 0.05% by mass or more and 1.00% by mass or less, and even more preferably 0.10% by mass or more and 0.70% by mass or less.

[0137] [2-1-2-6] Other ingredients The image-forming ink 2' may contain components other than those described above. Hereinafter, in this section, such components will also be referred to as "other components."

[0138] Other components include, for example, chelating agents, preservatives, mildew inhibitors, rust inhibitors, flame retardants, various dispersants, pH adjusters such as triethanolamine, antioxidants, ultraviolet absorbers, oxygen absorbers, dissolution aids, and penetrating agents.

[0139] Examples of chelating agents include ethylenediaminetetraacetate, etc. Examples of preservatives and antifungal agents include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one, 4-chloro-3-methylphenol, etc. Examples of rust inhibitors include benzotriazole, etc.

[0140] As the antiseptic / antifungal agent, for example, a compound having an isothiazolinone ring structure in the molecule can be suitably used.

[0141] The content of other components in the image-forming ink 2' is preferably 6.0% by mass or less, and more preferably 5.0% by mass or less.

[0142] [2-1-2-7] Other conditions The viscosity of the image-forming ink 2' at 25°C is preferably 2 mPa·s or more and 10 mPa·s or less, and more preferably 3 mPa·s or more and 8 mPa·s or less.

[0143] This makes it more difficult for nozzles of the inkjet head to become clogged, and improves the ejection stability of the image-forming ink 2'. Furthermore, even if the nozzles do become clogged, the nozzles can be capped to improve recovery.

[0144] The viscosity can be determined by measurement using a vibration viscometer, a rotational viscometer, a capillary viscometer, or a falling ball viscometer. For example, when using a vibration viscometer, the viscosity can be determined by measurement in accordance with JIS Z8809.

[0145] The surface tension of the image-forming ink 2' at 25°C is not particularly limited, but is preferably 20 mN / m or more and 60 mN / m or less, more preferably 25 mN / m or more and 50 mN / m or less, and even more preferably 27 mN / m or more and 40 mN / m or less.

[0146] This makes it more difficult for nozzles of the inkjet head to become clogged, and improves the ejection stability of the image-forming ink 2'. Furthermore, even if the nozzles do become clogged, the nozzles can be capped to improve recovery.

[0147] The surface tension can be measured by the Wilhelmy method or the Ring method using a surface tensiometer (e.g., DY-300, DY-500, DY-700, etc., manufactured by Kyowa Interface Science Co., Ltd.).

[0148] [2-1-3] Discharge by inkjet method The first layer 2 is formed by ejecting an image-forming ink 2' by an inkjet method onto a transfer medium 1 having a release layer 12. More specifically, the image-forming ink 2' is ejected so as to come into contact with the release layer 12 of the transfer medium 1.

[0149] Examples of inkjet methods include on-demand methods such as a charge deflection method, a continuous method, a piezoelectric method, and a bubble jet (registered trademark) method, but the piezoelectric method in which ink is ejected from an inkjet head using a piezoelectric vibrator is particularly preferred.

[0150] This makes it possible to more effectively prevent undesired alteration of the constituent components of the image-forming ink 2' in the inkjet head 50, and to improve the ejection stability by the inkjet method.

[0151] The inkjet head 50 may be a line head that performs printing by a line method, or a serial head that performs printing by a serial method.

[0152] In the line method using a line head, for example, an inkjet head having a width equal to or greater than the recording width of the transfer medium 1 is fixed to the recording device. Then, the transfer medium 1 is moved in the sub-scanning direction (the transport direction of the transfer medium 1), and ink droplets are ejected from the nozzles of the inkjet head 50 in conjunction with this movement, thereby forming a first layer 2 on the transfer medium 1.

[0153] In the serial method using a serial head, for example, an inkjet head 50 is mounted on a carriage that is movable in the width direction of the transfer medium 1. Then, the carriage is moved along the main scanning direction (width direction of the transfer medium 1), and ink droplets are ejected from the nozzles of the serial head, which is the inkjet head 50, in conjunction with this movement, thereby forming a first layer 2 on the transfer medium 1.

[0154] In this step, the first layer 2 is formed as a reverse image of the recording portion 4 to be formed on the transfer medium 5.

[0155] In this step, multiple types of image-forming inks 2' may be used. For example, a first image-forming ink containing a colorant of a color other than white and a second image-forming ink containing a white pigment may be used as the image-forming inks. After an image is formed using the first image-forming ink, another image may be formed using the second image-forming ink so as to overlap the first image. This improves the color development of the image.

[0156] Furthermore, for example, the first image forming ink may be a combination of at least two or more of black ink, cyan ink, magenta ink, and yellow ink.

[0157] [2-2] Second layer formation process In the second layer forming step, a treatment liquid 3' is ejected from an inkjet head 50' to form a second layer 3 so as to overlap the first layer 2 formed on the transfer medium 1 (1b).

[0158] [2-2-1] Processing liquid The processing liquid 3' is the processing liquid of the present invention. The treatment liquid 3' preferably satisfies the conditions described in [1] above. This provides the above-mentioned effects.

[0159] [2-2-2] Discharge by inkjet method The second layer 3 is formed by ejecting a treatment liquid 3' by an ink jet method onto the transfer medium 1 on which the first layer 2 has been formed.

[0160] Examples of inkjet methods include on-demand methods such as a charge deflection method, a continuous method, a piezoelectric method, and a bubble jet (registered trademark) method, but the piezoelectric method in which ink is ejected from an inkjet head using a piezoelectric vibrator is particularly preferred.

[0161] This makes it possible to more effectively prevent undesired denaturation of the components of the treatment liquid 3' in the inkjet head 50', and to improve the ejection stability by the inkjet method.

[0162] The inkjet head 50' may be a line head that performs printing by a line method, or a serial head that performs printing by a serial method.

[0163] In this step, the second layer 3 is formed so as to overlap the first layer 2, and in particular so as to have the same pattern as the first layer 2.

[0164] Furthermore, the first layer 2 and the second layer 3 may be formed using different inkjet recording devices, but are preferably formed using the same inkjet recording device.

[0165] Although it varies depending on the composition of the image-forming ink 2', the time from when the image-forming ink 2' is applied to the transfer medium 1 to when the treatment liquid 3' is applied is preferably at least 1 second and not more than 60 seconds, and more preferably at least 2 seconds and not more than 30 seconds. In this step, multiple types of image-forming inks 2' may be used.

[0166] [2-3] Drying process Between the second layer formation process described above and the thermal transfer process described below, there may be a further drying process (1c) for drying the transfer medium 1 on which the first layer 2 and the second layer 3 have been formed.

[0167] This makes it possible to more effectively prevent liquid components from unintentionally remaining in the final recorded matter 100 .

[0168] This step can be carried out, for example, by air drying, oven heating, or the like. When this process is carried out by air drying, the temperature of the atmosphere in which the transfer medium 1 on which the first layer 2 and the second layer 3 are formed is placed varies depending on the composition of the image-forming ink 2' and the treatment liquid 3', but is preferably 1°C or higher and 40°C or lower, and more preferably 5°C or higher and 30°C or lower.

[0169] When this process is carried out by air drying, the humidity of the atmosphere in which the transfer medium 1 on which the first layer 2 and the second layer 3 are formed is placed varies depending on the composition of the image-forming ink 2' and the treatment liquid 3', but is preferably 10% RH or more and 95% RH or less, and more preferably 20% RH or more and 90% RH or less.

[0170] When this process is carried out by air drying, the pressure of the atmosphere in which the transfer medium 1 on which the first layer 2 and the second layer 3 are formed is placed varies depending on the composition of the image-forming ink 2' and the treatment liquid 3', but is preferably 1 kPa or more and 150 kPa or less, and more preferably 10 kPa or more and 110 kPa or less.

[0171] When this process is carried out by heating, the temperature of the atmosphere in which the transfer medium 1 on which the first layer 2 and the second layer 3 are formed is placed varies depending on the composition of the image-forming ink 2' and the treatment liquid 3', but is preferably 80°C or higher and 220°C or lower, and more preferably 100°C or higher and 200°C or lower.

[0172] When this process is carried out by heating, the drying time varies depending on the composition of the image-forming ink 2' and the treatment liquid 3', but is preferably 0.2 minutes or more and 10 minutes or less, and more preferably 0.5 minutes or more and 5 minutes or less.

[0173] [2-4] Thermal transfer process In the thermal transfer process, the surface of the transfer medium 1 on which the first layer 2 and the second layer 3 are formed is heated while facing an absorbent transfer medium 5, thereby thermally transferring the first layer 2 and the second layer 3 to the transfer medium 5 and forming a recording section 4 on the transfer medium 5 (1d).

[0174] [2-4-1] Transfer medium The transfer medium 5 may be any absorbent material, such as various types of paper, porous metal, porous ceramics, porous glass, porous plastic, fabric, leather, etc., but fabric or leather is preferred.

[0175] This allows the printed matter to be transferred to the finished product after sewing the fabric or leather, regardless of the location, and provides good color development and abrasion resistance.

[0176] In particular, it is preferable that the transfer medium 5 is a fabric dyed with a dye. The material constituting the fabric is not particularly limited, and examples thereof include natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable fibers such as polylactic acid; and blends of these fibers are also possible.

[0177] The fabric may be any of the above-mentioned fibers in the form of woven fabric, knitted fabric, nonwoven fabric, etc., or may be a mixed weave.

[0178] In this embodiment, examples of the form of the fabric include cloth, clothing, and other accessories. Fabrics include, for example, woven fabrics, knitted fabrics, and nonwoven fabrics. Clothing and other accessories include, for example, sewn T-shirts, handkerchiefs, scarves, towels, carrier bags, cloth bags, curtains, sheets, bedspreads, wallpaper, and other furniture, as well as fabrics before and after cutting as parts before sewing. Examples of these forms include long rolls, cut pieces to a predetermined size, and finished products.

[0179] [2-4-2] Heating conditions The heating temperature in this step is not particularly limited, but is preferably 100°C or higher and 270°C or lower, more preferably 110°C or higher and 250°C or lower, and even more preferably 120°C or higher and 210°C or lower.

[0180] This more effectively prevents the constituent materials of the first layer 2 and the second layer 3 from unintentionally remaining on the transfer medium 1, while also saving energy and improving the productivity of the recorded matter 100.

[0181] When the glass transition temperature of the resin material constituting the resin particles contained in the treatment liquid 3' is Tg [°C] and the heating temperature in the thermal transfer process is Tp [°C], it is preferable to satisfy the relationship 70≦Tp−Tg≦290, it is more preferable to satisfy the relationship 95≦Tp−Tg≦260, and it is even more preferable to satisfy the relationship 110≦Tp−Tg≦210.

[0182] This more effectively prevents the constituent materials of the first layer 2 and the second layer 3 from unintentionally remaining on the transfer medium 1, while also saving energy and improving the productivity of the recorded matter 100.

[0183] The heating time in this step is not particularly limited, but is preferably from 5 to 90 seconds, more preferably from 15 to 70 seconds, and even more preferably from 20 to 60 seconds.

[0184] This more effectively prevents the constituent materials of the first layer 2 and the second layer 3 from unintentionally remaining on the transfer medium 1, while also saving energy and improving the productivity of the recorded matter 100.

[0185] This process can be carried out by any method, as long as the surface of the transfer medium 1 on which the first layer 2 and the second layer 3 are formed is heated while facing the absorbent transfer medium 5, but is preferably carried out by heat pressing.

[0186] This more effectively prevents the constituent materials of the first layer 2 and the second layer 3 from unintentionally remaining on the transfer medium 1, while also saving energy and improving the productivity of the recorded matter 100.

[0187] When this step is performed using a heat press, the pressure applied to the laminate of the transfer medium 1 and the transfer receiving medium 5 is 0.1 N / cm 2 More than 30N / cm 2 Preferably it is less than 0.6N / cm 2 More than 15N / cm 2 More preferably, it is 1.5 N / cm or less. 2 More than 5N / cm 2 More preferably, it is:

[0188] [2-5] Records Through the above steps, a recorded matter 100 is obtained (1e).

[0189] The recorded matter 100 obtained as described above has a recording portion 4 formed by a first layer 2 and a second layer 3.

[0190] It is preferable that at least a part of the recording portion 4 penetrates into the absorbent transfer medium 5 .

[0191] Normally, at least a portion of the recording section 4 is formed by integrating the constituent material of the first layer 2 with the constituent material of the second layer 3, but in the configuration shown, the entire recording section 4 is formed by integrating the constituent material of the first layer 2 with the constituent material of the second layer 3.

[0192] [3] Ink and treatment liquid set Next, the ink / treatment liquid set according to the present invention will be described. The ink / treatment liquid set according to the present invention comprises the image forming ink and treatment liquid described above.

[0193] More specifically, the ink / treatment liquid set according to the present invention preferably comprises an image-forming ink that satisfies the conditions described in [2-1-2] above, and also comprises the treatment liquid described in [1] above.

[0194] The ink / treatment liquid set according to the present invention may comprise at least one image-forming ink and one treatment liquid, but may also comprise multiple image-forming inks or multiple treatment liquids. Furthermore, the ink / treatment liquid set according to the present invention may further comprise other inks and treatment liquids in addition to the image-forming ink and treatment liquid that satisfy the above-mentioned conditions.

[0195] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these.

[0196] For example, in the above-described embodiment, the case where a drying step is performed between the second layer forming step and the thermal transfer step has been mainly described, but this drying step may be omitted. A drying step may be carried out between the first layer forming step and the second layer forming step.

[0197] In the above-described embodiment, after the first layer of the desired pattern is formed on the transfer medium, the treatment liquid is ejected to form the second layer of the desired pattern, and then the thermal transfer process is performed. However, in the present invention, multiple processes may be performed simultaneously. More specifically, for example, the ejection of the image forming ink and the ejection of the treatment liquid may be performed simultaneously on different parts of the same transfer medium. [Example]

[0198] Next, specific examples of the present invention will be described. [4] Preparation of ink for image formation (Preparation Example 1) By mixing the components in a predetermined ratio, an image-forming ink with the composition shown in FIG. 2 was obtained.

[0199] (Preparation Examples 2 and 3) An image-forming ink was prepared in the same manner as in Preparation Example 1, except that the types of components used in preparing the image-forming ink and the blending ratio of each component were changed to obtain the composition shown in Figure 2.

[0200] The compositions of the image-forming inks in Preparation Examples 1 to 3 are summarized in Figure 2. The "%" for each component in Figure 2 indicates the content in units of mass %. In Figure 2, CI Pigment Blue 15:3 is indicated as "PB15:3," a polyurethane resin with a glass transition temperature of -20°C (solid content of Takelac W6110, manufactured by Mitsui Chemicals, Inc.) is indicated as "polyurethane resin," a hot-melt resin (solid content of KT08701, manufactured by Unitika Ltd.) is indicated as "hot-melt resin," glycerin, a water-soluble organic solvent, is indicated as "Gly," and Silface SAG503A (manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant is indicated as "SAG503A." The image-forming inks in Preparation Examples 1 to 3 all contained resins with an average particle size ranging from 60 nm to 300 nm. Furthermore, the image-forming inks of Preparation Examples 1 to 3 all had a surface tension at 25° C. in the range of 30 mN / m to 40 mN / m, and a viscosity at 25° C. in the range of 3 mPa·s to 8 mPa·s. The surface tension was measured by the Wilhelmy method using a surface tensiometer (DY-300, manufactured by Kyowa Interface Science Co., Ltd.), and the viscosity was measured in accordance with JIS Z8809 using a vibration viscometer (VM-100, manufactured by Senicook Co., Ltd.).

[0201] [5] Preparation of processing solution (Example A1) By mixing the components in a predetermined ratio, a treatment liquid with the composition shown in FIG. 3 was obtained.

[0202] (Examples A2 to A16) A treatment liquid was prepared in the same manner as in Example A1, except that the types of components used in preparing the treatment liquid and the blending ratio of each component were changed to obtain the composition shown in Figures 3 and 4.

[0203] (Comparative examples A1 to A7) A treatment liquid was prepared in the same manner as in Example A1, except that the types of components used in preparing the treatment liquid and the blending ratio of each component were changed to obtain the composition shown in FIG.

[0204] The compositions of the treatment solutions of Examples A1 to A16 and Comparative Examples A1 to A7 are summarized in Figures 3 and 4. The numerical values ​​for each component in each Example and Comparative Example in Figures 3 and 4 indicate the content in units of mass%. In Figures 3 and 4, polyester resin (solid content of KT9204, manufactured by Unitika Ltd.) is referred to as "polyester dispersion resin," polyurethane resin (solid content of Takelac W6061, manufactured by Mitsui Chemicals, Inc.) is referred to as "polyurethane dispersion resin," BYK3420 (manufactured by BYK Japan KK) as a silicone surfactant is referred to as "BYK3420," and Olfine E1004 (manufactured by Nissin Chemical Industry Co., Ltd.) as an acetylene glycol surfactant that is not a silicone surfactant is referred to as "Olfine E1004." The treatment solutions of Examples A1 to A16 all contained resin particles with an average particle size ranging from 60 nm to 300 nm. Furthermore, the treatment liquids of Examples A1 to A16 all had a surface tension at 25° C. in the range of 30 mN / m to 40 mN / m, and a viscosity at 25° C. in the range of 3 mPa·s to 8 mPa·s. The surface tension was measured by the Wilhelmy method using a surface tensiometer (DY-300, manufactured by Kyowa Interface Science Co., Ltd.), and the viscosity was measured in accordance with JIS Z8809 using a vibration viscometer (VM-100, manufactured by Senicook Co., Ltd.).

[0205] [6] Production of recorded materials Example B1 First, a transfer medium (DTF print film manufactured by Inkmania Co., Ltd.) was prepared, which had a release layer made of a release agent provided on a base material made of polyethylene terephthalate.

[0206] Next, an inkjet recording device (Seiko Epson Corporation, SC-F2150) was filled with the image-forming ink obtained in Preparation Example 1 and the treatment liquid obtained in Example A1, and the image-forming ink was ejected from an inkjet head onto the surface of the transfer medium on which the release layer was provided, to form a first layer of a predetermined pattern.

[0207] Next, a treatment liquid was ejected from the inkjet head so as to overlap the first layer, forming a second layer having the same pattern as the first layer.

[0208] Next, the transfer medium on which the first and second layers were formed was dried by heating in an oven at 160° C. for 2 minutes.

[0209] Next, the surface of the transfer medium 1 on which the first and second layers were formed was placed opposite to a polyester fabric (Tropical, manufactured by Toray Industries, Inc.) which was an absorbent transfer medium, and the transfer medium was then subjected to a pressure of 0.5 N / m 2 The first layer and the second layer were thermally transferred onto the medium by heat pressing at 130° C. for 40 seconds under a pressure of 1.000 MPa. Thereafter, the transfer medium was removed to obtain a recorded product.

[0210] (Examples B2 to B15) Recorded matter was produced in the same manner as in Example B1, except that the types of image-forming ink and treatment liquid were changed as shown in FIGS.

[0211] (Example B16) A recorded material was produced in the same manner as in Example B1, except that the image-forming ink prepared in Preparation Example 1 was used, the treatment liquid was the same as in Example A16, cotton broadcloth (#4000) manufactured by Nisshinbo Co., Ltd. was used as the transfer medium, and the temperature during heat pressing was 170°C.

[0212] (Comparative examples B1 to B7) A recorded material was produced in the same manner as in Example B1, except that the types of image-forming ink, treatment liquid, and transfer medium were changed as shown in FIG.

[0213] The conditions for manufacturing the products of Examples B1 to B16 and Comparative Examples B1 to B7, i.e., the conditions for the recording method, are summarized in Figures 5 and 6. In Figures 5 and 6, Tropical (a polyester fabric manufactured by Toray Industries, Inc.) as a medium for receiving transfer is indicated as "PEs," and cotton broadcloth (#4000) manufactured by Nisshinbo Corporation as a medium for receiving transfer is indicated as "cotton."

[0214] [7] Evaluation The treatment solutions of Examples A1 to A16 and Comparative Examples A1 to A7, and the printed matter produced in Examples B1 to B16 and Comparative Examples B1 to B7 were evaluated as follows.

[0215] [7-1] Discharge stability Immediately after preparation, the treatment liquids of Examples A1 to A16 and Comparative Examples A1 to A7 were subjected to continuous printing stability evaluation as an evaluation of ejection stability.

[0216] First, each treatment liquid was filled into an inkjet printer (product name PX-G930, manufactured by Seiko Epson Corporation), and recording was performed on a recording medium (DTF print film manufactured by Inkmania). Specifically, a fill pattern that could be recorded at a resolution of 720 dpi horizontally and 720 dpi vertically at 100% duty was prepared and used. 100 A4-sized sheets were printed, and the presence or absence of warping and nozzle dropouts was checked and evaluated according to the following criteria.

[0217] A: Discharge is possible without any abnormalities. B: There is slight wrinkling and loss, but it is within the acceptable range. C: Significant wrinkling and loss have occurred.

[0218] [7-2] Transferability For Examples B1 to B16 and Comparative Examples B1 to B7, the state of the transfer medium after the recording portion was transferred to the transfer receiving medium was observed and evaluated according to the following criteria.

[0219] A: 100% of the image area printed on the transfer medium is transferred. B: 80% or more but less than 100% of the image area printed on the transfer medium is transferred. C: Less than 80% of the printed image area on the transfer medium has been transferred.

[0220] [7-3] Washing fastness The printed matter obtained in Examples B1 to B16 and Comparative Examples B1 to B7 was evaluated for washing fastness as follows.

[0221] Specifically, detergent was added to a household washing machine and rinsed repeatedly for 30 minutes, and the condition of each printed matter after each rinse was visually observed and evaluated according to the following criteria.

[0222] A: Even after rinsing 10 times, no peeling or chipping of the printed area was observed. B: After one rinse, slight peeling or chipping of the printed area occurs. C: Peeling or chipping of the printed area occurs significantly after one rinse.

[0223] [7-4] Migration The recorded materials obtained in Examples B1 to B16 and Comparative Examples B1 to B7 were visually observed for the occurrence of migration and evaluated according to the following criteria.

[0224] A: No migration is allowed at all. B: Slight migration is observed. C: Migration is evident.

[0225] These results are summarized in Figures 7 and 8. As is clear from Figures 7 and 8, excellent results were obtained in the present invention, whereas satisfactory results were not obtained in the comparative example. [Explanation of symbols]

[0226] 1...transfer medium, 11...substrate, 12...peeling layer, 2'...image forming ink, 2...first layer, 3'...treatment liquid, 3...second layer, 4...recording unit, 5...transfer receiving medium, 50...inkjet head, 50'...inkjet head, 100...recorded matter

Claims

1. A treatment liquid that is printed on a transfer medium and is composed of a material containing resin particles, a water-soluble organic solvent, a silicone surfactant, and water. The content of the resin particles is 5.0% by mass or more and 20.0% by mass or less, the water-soluble organic solvent contains a substance A and a substance B, The content of the substance A is 5.0% by mass or more and 20.0% by mass or less, The content of the substance B is 0.1% by mass or more and 3.0% by mass or less, A treatment liquid having an organic solvent content of 10.0 mass % or less, the organic solvent having a boiling point of more than 230°C. (However, the solubility of the substance A in water at 25°C is 1.00 [g / 100gH ２ and at least one compound selected from diols having a boiling point of 230°C or less, and the substance B has a solubility in water at 25°C of 0.10 [g / 100gH ２ O] or more 1.00[g / 100gH ２ 0] or less.)

2. The treatment liquid according to claim 1 , wherein the resin particles are made of a material containing at least one of a urethane resin and a polyester resin.

3. The treatment liquid according to claim 1 or 2, wherein the treatment liquid does not contain a coloring material.

4. a first layer forming step of forming a first layer by ejecting an image forming ink from an inkjet head onto a transfer medium having a release layer; a second layer forming step of ejecting a treatment liquid from an inkjet head to form a second layer so as to overlap the first layer; a thermal transfer step of thermally transferring the first layer and the second layer to an absorbent medium by heating the surface of the transfer medium on which the first layer and the second layer are formed while the surface is opposed to the absorbent medium, a processing liquid that is composed of a material containing resin particles, a water-soluble organic solvent, a silicone surfactant, and water, the content of the resin particles being 5.0% by mass or more and 20.0% by mass or less, the water-soluble organic solvent containing substance A and substance B, the content of substance A being 5.0% by mass or more and 20.0% by mass or less, the content of substance B being 0.1% by mass or more and 3.0% by mass or less, and the content of organic solvents having a boiling point of over 230°C being 10.0% by mass or less. (However, the solubility of the substance A in water at 25°C is 1.00 [g / 100gH ２ and at least one compound selected from diols having a boiling point of 230°C or less, and the substance B has a solubility in water at 25°C of 0.10 [g / 100gH ２ O] or more 1.00[g / 100gH ２ 0] or less.)

5. 5. The recording method according to claim 4, wherein a first image-forming ink containing a color material of a color other than white and a second image-forming ink containing a white pigment are used as the image-forming inks.

6. 6. The recording method according to claim 4, wherein the transfer medium is provided with an ink-receiving layer containing an inorganic oxide.

7. 6. The recording method according to claim 4, further comprising a drying step between the second layer forming step and the thermal transfer step, for drying the transfer medium on which the first layer and the second layer have been formed.

8. The recording method according to claim 4 or 5, wherein the thermal transfer step is carried out by a heat press.

9. 6. The recording method according to claim 4, wherein the medium is a fabric dyed with a dye.

10. The substance A contains both propylene glycol and 1,2-hexanediol, The substance B is 2,2'-butylethyl-1,3-propanediol, The content of propylene glycol in the treatment liquid is X ＰＧ [mass %], the content of 1,2-hexanediol in the treatment liquid is X ＨＤ When expressed as [mass %], 0.10≦X ＨＤ / X ＰＧ The relationship of ≦0.60 is satisfied, The content of the substance A in the treatment liquid is X Ａ [mass %], the content of the substance B in the treatment liquid is X Ｂ When expressed as [mass %], 0.01≦X Ｂ / X Ａ 6. The recording method according to claim 4, wherein the relationship of ≦0.60 is satisfied.

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