Printed article

Abstract

To provide a printed article in which a treatment agent containing a pigment, binder resin particles, and a silicone component adheres to an object to be printed, the printed article achieving favorable texture and rubbing fastness properties.SOLUTION: This printed article is a printed article in which a treatment agent containing a pigment, binder resin particles, and a silicone component adheres to an object to be printed, wherein the silicone component is present on both a front-side surface and a back-side surface of the printed article, and an amount of the silicone component on the back-side surface is smaller than that on the front-side surface.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a printed item in which a treatment agent containing a pigment, binder resin particles, and a silicone component is adhered to an object to be printed. [Background technology]

[0002] In the inkjet printing method, for example, an ink containing a pigment is used. In order to improve the abrasion fastness and the like of the object to be printed on which an image is formed (hereinafter, sometimes referred to as a printed item), the ink containing the pigment may be used together with a post-treatment liquid.

[0003] For example, Patent Document 1 describes an inkjet recording method performed on a low-absorbency or non-absorbency recording medium using a colored ink composition containing a colorant, a clear ink composition (corresponding to a post-treatment liquid) containing a resin, and a treatment liquid containing an aggregating agent that aggregates the components of the colored ink composition. Patent Document 1 also describes that the resin contained in the clear ink composition (corresponding to a post-treatment liquid) can protect the image and improve the abrasion resistance of the image. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-147307 Summary of the Invention

[0005] A printed item according to a first aspect of the present disclosure is a printed item in which a treatment agent containing a pigment, binder resin particles, and a silicone component is adhered to an object to be printed, The silicone component is present on both the front surface and the back surface of the print, and The amount of the silicone component is less on the back surface than on the front surface. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a printed item according to an embodiment of the present disclosure. [Figure 2] FIG. 2 is a side view showing an example of the configuration of a portion of an inkjet textile printing device that can be used to produce a printed item according to an embodiment of the present disclosure. [Figure 3] FIG. 3 is a perspective view showing an example of the overall configuration of an inkjet printer that can be used to produce a printed item according to an embodiment of the present disclosure. [Figure 4] FIG. 4 is a schematic cross-sectional view taken along line II-II in FIG. [Figure 5] FIG. 5 is an enlarged perspective view of the carriage shown in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0007] In recent years, there has been a demand for further improvement in the rub fastness of printed textiles in inkjet printing technology. Meanwhile, it has been found that the rub fastness of printed textiles can be further improved by treating the textile with a post-treatment liquid containing silicone oil. Specifically, silicone oil has a friction-reducing effect. Therefore, by coating the image formed on the textile with silicone oil, it is possible to obtain printed textiles with improved rub fastness properties.

[0008] However, it is expected that the rub fastness of printed textiles will vary depending on various factors, such as the type of silicone oil contained in the post-treatment liquid, the concentration of the silicone oil, the particle size of the emulsified particles containing the silicone oil, and the amount of the post-treatment liquid discharged (total amount discharged). Therefore, it would be advantageous to know the conditions for printed textiles with good rub fastness from the perspective of the structure of the printed textile itself after treating the printed textile with the post-treatment liquid. Note that Patent Document 1 also does not suggest at all the relationship between the structure of the printed textile itself after treating the printed textile with a clear ink composition (corresponding to the post-treatment liquid) and rub resistance.

[0009] In addition, in inkjet textile printing methods, not only ink containing a pigment is used, but also a pretreatment liquid is used as needed for the purpose of obtaining excellent color development, etc. However, when an image is formed on a textile to be printed using a pretreatment liquid and ink, the texture (touch, feel, etc.) of the printed textile deteriorates compared to the textile before image formation. Therefore, it is preferable to obtain a printed textile that has not only good rub fastness but also good texture.

[0010] The prints of the present disclosure have good hand and rub fastness properties.

[0011] In this disclosure, "a printed textile on which a treatment agent containing a pigment, binder resin particles, and a silicone component is adhered" refers to a printed textile in which an ink containing a pigment and binder resin particles and a post-treatment liquid containing a silicone oil from which the silicone component is derived are ejected, applied, or coated, in this order, onto a desired image formation area on the textile, using any method known to those skilled in the art, such as inkjet printing, spraying, or immersion, and then appropriately heated and dried. Optionally, the textile may be treated with a pre-treatment liquid prior to ejecting, applying, or coating the ink. In other words, in this disclosure, "treatment agent" does not refer to either the ink or the post-treatment liquid (or either the pre-treatment liquid, ink, or post-treatment liquid). In this disclosure, "treatment agent" refers to the treatment components in the ink and post-treatment liquid (or the pre-treatment liquid, ink, and post-treatment liquid) that remain after the production of the printed textile without volatilizing due to heating or other factors.

[0012] In the present disclosure, the "subject to be printed" is not particularly limited and may be a woven fabric or a knitted fabric. Examples of the subject to be printed include cotton fabric, silk fabric, linen fabric, polyester fabric, acetate fabric, rayon fabric, nylon fabric, polyurethane fabric, etc. Of these, the subject to be printed is preferably a polyester fabric.

[0013] In this disclosure, the term "silicone component" refers to a polymer having a siloxane bond as a skeleton, with organic groups, mainly composed of methyl groups, bonded to the silicon in the skeleton. Specifically, the term "silicone component" refers to a component of the silicone oil that originates from the silicone oil contained in the post-treatment liquid and remains after changing its form due to heat drying or the like after the post-treatment.

[0014] In the present disclosure, the "amount of silicone component" can be based on the detected amount of Si (mass%) that can be measured by quantitative analysis using energy dispersive X-ray spectroscopy (EDX) (hereinafter also referred to as "EDX"). That is, when comparing the amounts of silicone component, the amount of silicone component can be determined by comparing the detected amount of Si. Furthermore, in the present disclosure, the ratio of the amount of silicone component can also be determined by the detected amount of Si. In other words, the ratio (%) of the amount of silicone component means the ratio (%) of the detected amount of Si.

[0015] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. Note that the scope of the present disclosure is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present disclosure.

[0016] 1. Textile printing First, the configuration of a printed textile according to this embodiment will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a printed textile according to an embodiment of the present disclosure. As shown in FIG. 1, a treatment agent containing a pigment 1, binder resin particles 2, and a silicone component 3 (treatment components in the ink and post-treatment liquid (or pre-treatment liquid, ink, and post-treatment liquid) remaining after production of the printed textile) is attached to an image formation region 10PR of the printed textile 10. The pigment 1 and binder resin particles 2 are components derived from the ink. The silicone component 3 is a component derived from the silicone oil contained in the post-treatment liquid. The ink and the post-treatment liquid containing silicone oil will be described in detail in "2. Method for producing a printed textile" below. When the printed textile 10 is viewed from the direction of the arrow shown in FIG. 1, an image formed on the printed textile 10 can be confirmed.

[0017] As shown in FIG. 1, the silicone component 3 is present on both the front surface 10Sf of the printed material and the back surface 10Sb of the printed material in the image forming region 10PR.

[0018] In the present disclosure, the "front surface of the printed textile" refers to the surface of the printed textile onto which ink and post-treatment liquid (or pre-treatment liquid, ink, and post-treatment liquid) are ejected, etc., in the image formation area of ​​the printed textile. When the amount of detected Si is measured by quantitative analysis using EDX, the "front surface of the printed textile" refers to the area near the front surface of the printed textile, measured under conditions described in detail in the Examples below. On the other hand, the "back surface of the printed textile" refers to the surface opposite the surface of the printed textile onto which ink and post-treatment liquid (or pre-treatment liquid, ink, and post-treatment liquid) are ejected, etc., in the image formation area of ​​the printed textile. Similarly, when the amount of detected Si is measured by quantitative analysis using EDX, the "back surface of the printed textile" refers to the area near the back surface of the printed textile, measured under conditions described in detail in the Examples below. Furthermore, in the present disclosure, the "internal layer portion between the front and back surfaces of the printed textile" refers to the internal portion of the printed textile sandwiched between them.

[0019] Furthermore, in the present disclosure, "a silicone component is present on the front surface (or back surface) of the printed item" means that Si is detected on the front surface (or back surface) of the printed item by quantitative analysis using EDX, as will be described in detail in the Examples below.

[0020] As shown in FIG. 1 , in the printed item 10 according to this embodiment, the amount of silicone component 3 is less on the back surface 10Sb of the printed item than on the front surface 10Sf of the printed item. This gradient of silicone component 3 decreasing from the front surface to the back surface of the printed item 10 provides the printed item 10 with good texture and rub fastness properties. Specifically, the penetration of silicone component 3 from the front to the back of the printed item can improve the texture and rub resistance of the printed item. Furthermore, by reducing the amount of silicone component 3 on the back side and ensuring a sufficient amount of silicone component 3 on the front side, the front side of the printed item 10 on which the image is formed has excellent rub fastness. Furthermore, a low amount of silicone component 3 on the back side is expected to maintain good water absorbency on the back side of the printed item 10. However, if the amount of silicone component 3 on the back side is excessively low, the texture of the printed item 10 may be inferior in some cases.

[0021] The ratio of the amount of silicone component 3 on the back surface 10Sb of the printed product to the amount of silicone component 3 on the front surface 10Sf of the printed product is preferably 70% or less. When the ratio of the amount of silicone component 3 is 70% or less, the rub fastness of the printed product 10, particularly wet rub fastness, can be improved. Furthermore, the lower limit of the ratio of the amount of silicone component 3 on the back surface 10Sb of the printed product to the amount of silicone component 3 on the front surface 10Sf of the printed product is not particularly limited, but is preferably greater than 15%. When the ratio of the amount of silicone component 3 is greater than 15%, the printed product 10 reliably has a good texture. Note that the degree of its inherent texture (touch, feel, etc.) varies depending on the type of printed object. Therefore, the degree of texture of the printed product 10 when the ratio of the amount of silicone component 3 is greater than 15% may also vary depending on the type of printed object.

[0022] The proportion of the amount of such silicone component 3 is more preferably 68% or less, even more preferably 66% or less, and particularly preferably a value selected from the group consisting of 65%, 63%, 62%, 60%, 58%, 56%, 54%, 52%, 50%, 49%, and 48%. The proportion of the amount of such silicone component 3 is more preferably 20% or more, even more preferably 23% or more, and particularly preferably a value selected from the group consisting of 25%, 27%, 30%, 31%, 32%, 33%, 34%, 37%, 39%, 41%, 44%, and 46%. Specifically, the proportion of the amount of silicone component 3 is preferably 31% to 60%, more preferably 33% to 60%, and particularly preferably 46% to 60%. By setting the proportion in this range, the printed product can be more reliably provided with good texture and rubbing fastness (particularly wet rubbing fastness).

[0023] Furthermore, as shown in FIG. 1, in the printed matter 10 according to this embodiment, it is preferable that the pigment 1 is present on the front surface 10Sf of the printed matter and in the inner layer portion 10M of the printed matter between the front surface 10Sf of the printed matter and the back surface 10Sb of the printed matter.

[0024] In this disclosure, "the pigment is present (or not present) on the front surface of the printed material and in the inner layer portion between the front surface and the back surface of the printed material" means that, as will be described in detail in the Examples below, when a cross section of the image-forming area of ​​the printed material is observed using an optical microscope, the pigment can be confirmed (or not confirmed) by visual inspection on the front surface of the printed material and in the inner layer portion of the printed material.

[0025] When the pigment 1 is present on the front surface 10Sf of the printed material and on the inner layer portion 10M of the printed material, the color of the image formed on the printed material 10 becomes vivid.

[0026] Furthermore, in the printed textile 10 according to this embodiment, as shown in FIG. 1, it is more preferable that the pigment 1 is not present on the back surface 10Sb of the printed textile. If the pigment 1 is not present on the back surface 10Sb of the printed textile, the color of the image on the printed textile 10 can be made more vivid. In such a case, it is also expected that the texture on the back side of the printed textile 10 can be made better. Furthermore, in the printed textile 10 according to this embodiment, as shown in FIG. 1, it is preferable that the silicone component 3 is present in the image forming region 10PR in an area on the back surface 10Sb of the printed textile that faces the area on the front surface 10Sf of the printed textile where the pigment 1 is present. In other words, it is preferable that the penetration of the ink (pigment 1) into the vicinity of the back surface of the printed textile is suppressed in the image forming region 10PR, while the post-treatment liquid (silicone component 3) penetrates around the ink.

[0027] A penetration gradient in which the amount of silicone component decreases from the front surface to the back surface of the printed textile can be formed by selecting an appropriate method for ejecting, applying, or coating the ink and post-treatment liquid (or pre-treatment liquid, ink and post-treatment liquid). For example, inkjet printing or spraying can be used to create a printed textile with such a penetration gradient of silicone components. In particular, when the ink and post-treatment liquid (or pre-treatment liquid, ink and post-treatment liquid) are ejected onto the printing target using wet-on-wet inkjet printing, the post-treatment liquid is ejected before the ink (or ink and pre-treatment liquid) dries. In this case, penetration of the ink (pigment 1) is easily suppressed, making it easier to ultimately create a printed textile with the aforementioned penetration gradient of silicone components.

[0028] Furthermore, as will be described in the examples below, the ratio of the amount of the silicone component described above is not controlled solely by factors such as the ejection amount (total ejection amount), imparting amount (total imparting amount), and coating amount (total coating amount) of the post-treatment liquid. Specifically, when producing a printed textile, the ejection amount and total ejection amount of the post-treatment liquid per ejection, the ejection interval of the ink and the post-treatment liquid, the type of pigment in the ink, the ink physical properties such as content, the silicone oil content in the post-treatment liquid, and the physical properties of the post-treatment liquid such as viscosity of the post-treatment liquid can be appropriately adjusted to control the ratio of the amount of silicone component on the back surface to the front surface of the printed textile within the above numerical range. From the viewpoint of ease of control of the ratio of the amount of silicone component, the printed textile according to this embodiment is preferably an inkjet printed textile produced by applying an inkjet printing method.

[0029] Similarly, inkjet printing or spray printing, especially wet-on-wet inkjet printing, can easily produce textile prints in which the pigment is present on both the front surface and the inner layer of the print. This is thought to be because the post-treatment liquid is ejected before the ink (or ink and pre-treatment liquid) dries, preventing the pigment from penetrating to the back surface of the print. Furthermore, similarly, the location of the pigment can be precisely controlled by appropriately adjusting the ink ejection volume, total ejection volume, application volume, and total application volume, while taking into consideration the type of textile to be printed, the type of pigment in the ink, its physical properties (e.g., pigment content), the silicone oil content in the post-treatment liquid, and its physical properties (e.g., viscosity).

[0030] 2. How to make printed items Next, an example of a method for producing a printed item according to this embodiment will be specifically described.

[0031] The printed textile according to this embodiment can be produced by ejecting, applying, or coating the ink and a post-treatment liquid containing silicone oil in this order onto a desired image formation area on a subject to be printed using any method known to those skilled in the art, such as inkjet printing, spraying, or immersion, followed by appropriate heating and drying. Optionally, the subject to be printed may be treated with a pre-treatment liquid prior to ejecting, applying, or coating the ink. First, the optionally used pre-treatment liquid, as well as the ink and post-treatment liquid, will be described below.

[0032] (Pretreatment liquid) The optionally used pretreatment liquid is not particularly limited as long as it is any pretreatment liquid known to those skilled in the art, and includes, for example, a cationic polymer, an aqueous solvent, and optional components (e.g., surfactants, etc.).

[0033] The pretreatment liquid is ejected, applied, or coated onto the object to be printed prior to the ink being ejected, etc. The cationic polymer contained in the pretreatment liquid reacts with and aggregates with the pigment contained in the ink that is subsequently ejected, etc., thereby ensuring excellent color development (image density).

[0034] The cationic polymer contained in the pretreatment liquid may be any cationic polymer that is positively charged. Examples of cationic polymers include ammonium-containing polymers, amine-containing polymers, polyallylamine, polyvinylamine, polyimine, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyridine, aminoacetalized polyvinyl alcohol, ionene polymers, polyvinylimidazole, polyvinylbenzylphosphonium, polyalkylallylammonium, polyamidine, and polyamine sulfone. Among these, from the viewpoint of obtaining superior color development, the cationic polymer preferably includes one or more selected from the group consisting of quaternary ammonium-containing polymers, diallyldimethylammonium sulfur dioxide copolymers, diallyldimethylammonium chloride acrylamide copolymers, diallyldimethylammonium chloride polymers, dimethylamine-ammonia-epichlorohydrin polycondensates, and dimethylamine-ammonia-epichlorohydrin polycondensates.

[0035] The weight-average molecular weight of the cationic polymer is not particularly limited, but is preferably about 1000 to 10000. The content of the cationic polymer is not particularly limited, but is preferably 0.3% by mass or more and 35% by mass or less, based on the total mass of the pretreatment liquid.

[0036] The aqueous solvent contained in the pretreatment liquid is not particularly limited, but typically consists of water or water and an organic solvent.

[0037] The organic solvent is not particularly limited, but examples thereof include glycols, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, ethers, vegetable oils, etc. Examples of water-soluble organic solvents include polyhydric alcohols, ether compounds of polyhydric alcohols, nitrogen-containing compounds, alcohol compounds, sulfur-containing compounds, propylene carbonate, ethylene carbonate, etc. Among these, it is preferable to use glycols such as propylene glycol. These can be used alone or in combination of two or more.

[0038] When the pretreatment liquid contains an organic solvent, the content thereof is preferably 3% by mass or more and 50% by weight or less relative to the total mass of the pretreatment liquid.

[0039] Furthermore, the pretreatment liquid may contain a surfactant for the purpose of adjusting the surface tension to an appropriate level. Usable surfactants are not particularly limited, but examples include nonionic surfactants, cationic surfactants, and anionic surfactants. When the pretreatment liquid contains a surfactant, its content is preferably 0.1% by mass or more and 5% by mass or less, based on the total mass of the pretreatment liquid.

[0040] The pretreatment liquid may contain other additives as needed, such as a dissolution stabilizer, a drying inhibitor, an antioxidant, a viscosity adjuster, a pH adjuster, and an anti-mold agent.

[0041] The pretreatment solution can be prepared by any method known to those skilled in the art. For example, a column is first filled with a basic ion exchange resin, and a cationic polymer is passed through the resin to obtain a regulated cationic polymer with a reduced halogen ion concentration. The regulated cationic polymer is then mixed with an aqueous solvent and optional components (e.g., surfactants) to obtain a pretreatment solution.

[0042] (ink) The ink is not particularly limited as long as it contains a pigment and binder resin particles and is known to those skilled in the art. For example, the ink contains a pigment, binder resin particles, and an aqueous medium. If necessary, the ink may further contain at least one selected from the group consisting of a surfactant and a polyol. These components are described below.

[0043] The pigment is dispersed in an aqueous medium. From the viewpoint of obtaining an ink excellent in image density, hue, and color stability, the D 50 In the present disclosure, the volume median diameter (D50 The measured value of (a) is the median diameter measured using a laser diffraction / scattering particle size distribution measuring device (LA-950 manufactured by Horiba, Ltd.).

[0044] Examples of pigments include yellow pigments, orange pigments, red pigments, blue pigments, purple pigments, and black pigments. Yellow pigments include, for example, CI Pigment Yellow (74, 93, 95, 109, 110, 120, 128, 138, 139, 151, 154, 155, 173, 180, 185, and 193). Orange pigments include, for example, CI Pigment Orange (34, 36, 43, 61, 63, and 71). Red pigments include, for example, CI Pigment Red (122 and 202). Blue pigments include, for example, CI Pigment Blue (15, more specifically 15:3). Purple pigments include, for example, CI Pigment Violet (19, 23, and 33). Black pigments include, for example, CI Pigment Black (7).

[0045] The pigment content is preferably 1% by mass or more and 12% by mass or less relative to the total mass of the ink. A pigment content of 1% by mass or more can improve the image density of the resulting printed textile. Furthermore, a pigment content of 12% by mass or less can provide an ink with high fluidity.

[0046] The aqueous medium contained in the ink is a medium containing water as its main component. The aqueous medium may function as a solvent or as a dispersion medium. Specific examples of the aqueous medium include water and a mixture of water and a polar solvent. Examples of polar solvents contained in the aqueous medium include methanol, ethanol, isopropyl alcohol, butanol, and methyl ethyl ketone. The water content in the aqueous medium is preferably 90% by mass or more, and particularly preferably 100% by mass. The content of the aqueous medium is preferably 5% by mass or more and 70% by mass or less, and more preferably 40% by mass or more and 60% by mass or less, relative to the total mass of the ink.

[0047] The binder resin particles exist in the form of particles dispersed in an aqueous medium. The binder resin particles function as a binder that binds the subject to be printed and the pigment. Therefore, when the ink contains binder resin particles, it is possible to obtain a printed product with excellent pigment fixation.

[0048] Examples of the resin contained in the binder resin particles include urethane resin, (meth)acrylic resin, styrene-(meth)acrylic resin, styrene-maleic acid copolymer, vinylnaphthalene-(meth)acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, etc. The resin contained in the binder resin particles is preferably a urethane resin.

[0049] The content of binder resin particles is preferably 1% by mass or more and 20% by mass or less relative to the total mass of the ink. When the content of binder resin particles is 1% by mass or more, a printing object with excellent pigment fixation can be obtained. On the other hand, when the content of binder resin particles is 20% by mass or less, the ink can be stably ejected onto the printing object.

[0050] When the ink contains a surfactant, the ink's wettability to the printing target is improved. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. The surfactant contained in the ink is preferably a nonionic surfactant. The nonionic surfactant is preferably a surfactant having an acetylene glycol structure, and more preferably an acetylene diol ethylene oxide adduct. The HLB value of the surfactant is preferably 3 or more and 20 or less. The HLB value of the surfactant is calculated, for example, by the Griffin method using the formula "HLB value = 20 × (sum of formula weights of hydrophilic moieties) / molecular weight." To improve image density while suppressing image offset, the content of the surfactant is preferably 0.1% by mass to 5.0% by mass, and more preferably 0.5% by mass to 2.0% by mass, relative to the mass of the ink.

[0051] The viscosity of the ink can be suitably adjusted by including a polyol in the ink, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, or glycerin.

[0052] The ink may further contain known additives (more specifically, a dissolution stabilizer, an anti-drying agent, an antioxidant, a viscosity adjuster, a pH adjuster, an anti-mold agent, etc.) as needed.

[0053] The ink can be prepared by any method known to those skilled in the art. For example, the ink can be prepared by mixing the pigment, binder resin particles, aqueous medium, and optional components (e.g., surfactant, polyol, etc.) using a mixer. The mixing time is, for example, from 1 minute to 30 minutes.

[0054] (Post-processing liquid) The post-treatment liquid is not particularly limited as long as it is any post-treatment liquid containing silicone oil and known to those skilled in the art. The post-treatment liquid contains, for example, emulsified particles containing silicone oil, an aqueous medium, and components added as needed (e.g., acid, base, polyol, dispersant, etc.). The emulsified particles are dispersed in the aqueous medium of the post-treatment liquid. That is, the post-treatment liquid is an emulsion, more specifically, an oil-in-water (O / W) emulsion.

[0055] The average particle size of the silicone oil-containing emulsion particles (particle size dispersed in an aqueous medium) is preferably 100 nm or more and 250 nm or less. By setting the average particle size of the emulsion particles to 100 nm or more and 250 nm or less, the post-treatment liquid can produce a printed product with better texture and superior rub fastness, and also exhibits excellent ejection properties from the processing head of an inkjet printing device. The average particle size of the emulsion particles refers to the harmonic mean particle size (also called the cumulant mean particle size) calculated based on scattered light intensity using the cumulant method. The average particle size of the emulsion particles is measured in accordance with the method specified in ISO 13321:1996 (Particle size analysis - Photon correlation spectroscopy).

[0056] The silicone oil contained in the emulsified particles is one or more of an ionic group-containing silicone oil and a non-modified silicone oil. The ionic group-containing silicone oil and the non-modified silicone oil will be described below.

[0057] The ionic group-containing silicone oil is a modified silicone oil, more specifically, an ionic group-modified silicone oil. Examples of the ionic group-modified silicone oil include a modified silicone oil having an ionic group introduced into a side chain and a modified silicone oil having an ionic group introduced into a terminal group.

[0058] The modified silicone oil having an ionic group introduced into the side chain has a first terminal group represented by the following formula (1a), a repeating unit represented by the following formula (1b), a repeating unit represented by the following formula (1c), and a second terminal group represented by the following formula (1d).

[0059] [ka]

[0060] The * in formula (1a) represents a bond bonded to a silicon atom in the repeating unit represented by formula (1b) or (1c). The * in formula (1d) represents a bond bonded to an oxygen atom in the repeating unit represented by formula (1b) or (1c). R in formula (1c) 1 represents a group containing an ionic group. The ionic group of the group containing an ionic group is preferably an amino group, a carboxy group, a phenolic hydroxy group, or a silanol group.

[0061] The modified silicone oil having an ionic group introduced into the terminal group has a first terminal group represented by the following formula (2a), a repeating unit represented by the following formula (2b), and a second terminal group represented by the following formula (2c).

[0062] [ka]

[0063] The * in formula (2a) represents a bond bonded to a silicon atom in the repeating unit represented by formula (2b). The * in formula (2c) represents a bond bonded to an oxygen atom in the repeating unit represented by formula (2b). R in formula (2a) 2 , and R in formula (2c) 3 each independently represents a group containing an ionic group. The ionic group of the group containing an ionic group is preferably an amino group, a carboxy group, a phenolic hydroxy group, or a silanol group.

[0064] The ionic group-containing silicone oil preferably contains at least one selected from the group consisting of amino-modified silicone oil, carboxy-modified silicone oil, phenol-modified silicone oil, and silanol-modified silicone oil.

[0065] In order to disperse emulsion particles containing ionic group-containing silicone oils in an aqueous medium, the functional group equivalent of the ionic group-containing silicone oil is preferably 1000 g / mol to 5500 g / mol, where the functional group equivalent is the molecular weight per 1 mol of functional group (ionic group).

[0066] An example of the non-modified silicone oil is dimethylpolysiloxane.

[0067] The content of silicone oil in the post-treatment liquid is preferably 5% by mass or more and 15% by mass or less. A silicone oil content of 5% by mass or more can improve the texture of the printed textile and produce a printed textile with better rub fastness. A silicone oil content of 15% by mass or less can improve the ejection properties of the post-treatment liquid from the processing head.

[0068] The viscosity of silicone oil is 500mm 2 / s (i.e. mm 2 / sec) or more. 2 / s or more, the silicone oil is less likely to be detached from the printed material due to friction, and a printed material with excellent dry rub fastness and wet rub fastness can be produced. The viscosity of the silicone oil means the kinematic viscosity at 25°C, and is measured in accordance with the method described in JIS (Japanese Industrial Standards) Z8803:2011 (Method for measuring viscosity of liquids). For example, the silicone oil can be extracted from the post-treatment liquid with toluene, washed, and dried to separate the silicone oil from the post-treatment liquid, and the viscosity of the silicone oil can be measured.

[0069] The aqueous medium contained in the post-treatment liquid is a medium containing water as a main component. The aqueous medium may function as a solvent or as a dispersion medium. Specific examples of the aqueous medium include water and a mixture of water and a polar solvent. Examples of polar solvents contained in the aqueous medium include methanol, ethanol, isopropyl alcohol, butanol, and methyl ethyl ketone. The water content in the aqueous medium is preferably 90% by mass or more. The content of the aqueous medium is preferably 50% by mass or more and 90% by mass or less relative to the total mass of the post-treatment liquid.

[0070] The post-treatment liquid may further contain an acid, a base, a polyol, etc., as required.

[0071] Examples of the acid include strong acids such as hydrochloric acid, paratoluenesulfonic acid, sulfuric acid, etc., and weak acids such as benzoic acid, acetic acid, etc. Examples of the base include sodium hydroxide.

[0072] When the post-treatment liquid contains a polyol, the viscosity of the post-treatment liquid can be suitably adjusted. As in the case of the ink described above, examples of polyols contained in the post-treatment liquid include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and glycerin.

[0073] The preparation method of post-treatment liquid can be any method known to those skilled in the art.For example, use a homogenizer to mix silicone oil, aqueous medium, and optionally added components (for example, acid or base and polyol) to emulsify.In this way, the emulsified particles containing silicone oil are dispersed in aqueous medium, and post-treatment liquid can be obtained.

[0074] To ensure that the emulsification proceeds smoothly, a raw emulsion containing emulsified particles may be prepared in advance, and the raw emulsion, an aqueous medium, and, if necessary, a polyol may be mixed to obtain the post-treatment liquid. The raw emulsion may contain, for example, silicone oil, a portion of the aqueous medium, and an acid or base added as necessary. In preparing the raw emulsion, the emulsification time is, for example, 5 minutes to 1 hour. The emulsification temperature is, for example, 5°C to 40°C. The content of the raw emulsion is, for example, 15% by mass to 50% by mass relative to the total mass of the post-treatment liquid.

[0075] Next, as an example of the method for producing a printed item according to this embodiment, a method for producing a printed item using a flatbed inkjet printing device will be specifically described with reference to FIG.

[0076] Fig. 2 shows a side view of an example of the configuration of a portion of an inkjet textile printing apparatus that can be used to produce a printed item according to an embodiment of the present disclosure. For ease of understanding, Fig. 2 mainly shows each component in a schematic manner. The size, number, etc. of each component shown in the figure may be changed as appropriate.

[0077] A flatbed type inkjet printing apparatus (part) 20 shown in FIG. 2 ejects the above-mentioned pretreatment liquid, ink, and posttreatment liquid onto the object P to be printed.

[0078] 2 includes an ink head 4, a pre-treatment liquid head 5, a post-treatment liquid head 6, and a mounting table 7. The ink head 4 has a first ink head 4a, a second ink head 4b, a third ink head 4c, and a fourth ink head 4d.

[0079] The pretreatment liquid head 5 and the posttreatment liquid head 6 eject the pretreatment liquid and the posttreatment liquid, respectively, onto at least the image formation area of ​​the printing object P. The pretreatment liquid head 5 and the posttreatment liquid head 6 are not particularly limited, but examples thereof include a piezo type head and a thermal inkjet type head.

[0080] The ink head 4 ejects ink onto an image forming area of ​​the printing object P. The first ink head 4a, second ink head 4b, third ink head 4c, and fourth ink head 4d of the ink head 4 each eject ink of a different color. There are no particular limitations on the ink head 4, but examples include a piezoelectric head and a thermal inkjet head.

[0081] The printing object P is placed on the mounting table 7. A pretreatment liquid head 5, an ink head 4, and a posttreatment liquid head 6 are disposed above the mounting table 7 so that the pretreatment liquid, ink, and posttreatment liquid can be ejected onto the printing object P. Driven by a motor (not shown), the mounting table 7 moves horizontally in a direction from the pretreatment liquid head 5 toward the posttreatment liquid head 6 (for example, to the right in FIG. 1). The horizontal movement of the mounting table 7 transports the printing object P on the mounting table 7.

[0082] In producing a printed item, first, the mounting table 7 on which the object to be printed P is placed moves horizontally, and the object to be printed P is transported to a position facing the pretreatment liquid head 5. The pretreatment liquid head 5 ejects the pretreatment liquid onto the object to be printed P. The pretreatment liquid head 5 may eject the pretreatment liquid only onto the image formation area of ​​the object to be printed P, or onto an area wider than the image formation area of ​​the object to be printed P, or onto the entire surface of the object to be printed P. In order to reduce the amount of pretreatment liquid used and prevent deterioration in the texture of the printed item, it is preferable that the pretreatment liquid head 5 ejects the pretreatment liquid only onto the image formation area of ​​the object to be printed P.

[0083] After the pretreatment liquid is ejected from the pretreatment liquid head 5, the object to be printed P is transported to a position opposite the ink head 4. Ink is ejected from the ink head 4 onto the image formation area of ​​the object to be printed P. It is preferable to adjust the ink ejection amount (ejection amount per ejection and total ejection amount) appropriately so that a printed object is ultimately obtained in which the pigment is present on the front surface and in the inner layer of the printed object. Similarly, it is preferable to adjust the ink ejection amount (ejection amount per ejection and total ejection amount) appropriately so that a printed object is ultimately obtained in which the pigment is not present on the back surface of the printed object. The ink ejection amount (ejection amount per ejection and total ejection amount) onto the object to be printed P needs to be appropriately adjusted while taking into consideration factors such as the type of object to be printed P, the type and content of the pigment in the ink, the ink's physical properties, the ejection amount per ejection and total ejection amount of the posttreatment liquid (described below), the silicone oil content in the posttreatment liquid, and the physical properties of the posttreatment liquid, such as the viscosity of the posttreatment liquid. For example, the ink ejection amount (total ejection amount) is preferably 5 g / m 2 More than 40g / m 2Less than 10 g / m, more preferably 2 More than 40g / m 2 More preferably, 20 g / m or less 2 More than 40g / m 2 In this way, an image is formed with ink in the image formation area of ​​the printing object P. After the ink is ejected, the mounting table 7 on which the printing object P is placed further moves horizontally, and the printing object P is transported to a position facing the post-treatment liquid head 6.

[0084] The post-treatment liquid head 6 ejects the post-treatment liquid onto at least the image formation area of ​​the object to be printed P. The post-treatment liquid head 6 may eject the post-treatment liquid only onto the image formation area of ​​the object to be printed P. Alternatively, the post-treatment liquid head 6 may eject the post-treatment liquid onto an area wider than the image formation area of ​​the object to be printed P. In this case, it is necessary to adjust the ejection amount of the post-treatment liquid (the amount ejected per ejection and the total amount ejected) to an appropriate amount so as to form a penetration gradient in which the amount of silicone component decreases from the front side to the back side of the printed item. Furthermore, as described above, it is preferable to adjust the ejection amount of the post-treatment liquid (the amount ejected per ejection and the total amount ejected) so as to form a penetration gradient in which the ratio of the amount of silicone component on the back side surface to the front side surface of the printed item is 70% or less. The amount of post-treatment liquid ejected onto the object P to be printed (amount ejected per time and total amount ejected) must be adjusted appropriately while taking into consideration factors such as the type of object P to be printed, the amount of ink ejected per time and total amount ejected, the type of pigment in the ink, the ink properties such as content, the silicone oil content in the post-treatment liquid, and the viscosity and other properties of the post-treatment liquid. For example, the amount of post-treatment liquid ejected (total amount ejected) is preferably 2 g / m 2 More than 100g / m 2 less than 3 g / m 2 More than 60g / m 2 or less, more preferably 4 g / m 2 More than 45g / m 2 Below 5 g / m, particularly preferably 2 More than 40g / m 2 In this way, a treatment film is formed by the post-treatment liquid on the image formed in the image formation area of ​​the printing object P.

[0085] After the post-treatment liquid head 6 ejects the post-treatment liquid onto the object P to be printed, the mounting table 7 on which the object P is placed further moves horizontally, transporting the object P to a position facing a heating unit (not shown). The heating unit heats the object P to be printed, drying the pre-treatment liquid, ink, and post-treatment liquid. The heating temperature is, for example, 120°C or higher and 180°C or lower. The heating time is, for example, 1 minute or higher and 10 minutes or lower. Heating evaporates volatile components contained in the pre-treatment liquid, ink, and post-treatment liquid, promoting fixation of the pre-treatment liquid, ink, and post-treatment liquid to the object P to be printed, and forming an ink image. As a result, a printed item is produced in which a treatment agent containing a pigment, binder resin particles, and a silicone component is adhered to the object P to be printed, and which has a penetration gradient such that the amount of silicone component decreases from the front side to the back side of the printed item.

[0086] The printed item produced in this way has a penetration gradient of the silicone component as shown in Figure 1, and therefore has good texture and rub fastness properties.

[0087] The above-described method for producing a printed item is merely an example, and the following modifications may be mentioned.

[0088] As a first modification, instead of using the post-treatment liquid head 6 provided in the inkjet printing apparatus 20, a spray or the like for applying the post-treatment liquid may be used to form a penetration gradient of the amount of silicone component.

[0089] As a second modified example, the inkjet printing apparatus 20 does not have to include the pretreatment liquid head 5, and the pretreatment liquid does not have to be ejected, applied, or coated onto the object P to be printed.

[0090] As a third modified example, in the inkjet printing apparatus 20, although the mounting table 7 moves horizontally in the example of the above-described manufacturing method, the pretreatment liquid head 5, the ink head 4, and the posttreatment liquid head 6 may move horizontally while the mounting table 7 is fixed, and any one of the pretreatment liquid, the ink, and the posttreatment liquid may be ejected.

[0091] As a fourth modification, the printed material according to this embodiment may be produced using an inkjet printing device that is not of the flatbed type.

[0092] 3. Recording equipment used in the production of textile prints Finally, an example of the overall configuration of an inkjet printer (recording device) that can be used to produce the printed textile according to this embodiment will be described with reference to the drawings.

[0093] Fig. 3 shows a perspective view of an example of the overall configuration of an inkjet printer that can be used to produce a printed textile according to an embodiment of the present disclosure. The inkjet printer 1000 shown in Fig. 3 is suitable for use in digital textile printing, which uses an inkjet method to print images such as letters and patterns on a textile object made of fabric such as woven or knitted fabric. Alternatively, the inkjet printer 1000 may be used to print various images on a textile object such as a paper sheet or a resin sheet. Fig. 4 is a schematic cross-sectional view taken along line II-II in Fig. 3.

[0094] The inkjet printer 1000 is a printer that prints images on a wide and long workpiece W (subject to be printed) using an inkjet method. As an example, the width of the workpiece W is several meters, and the inkjet printer 1000 includes an apparatus frame 100, and a workpiece transport unit 200 and a carriage 30 that are incorporated into this apparatus frame 100. In the inkjet printer 1000 shown in FIG. 3, the left-to-right direction is the main scanning direction S (see FIG. 5) when printing on the workpiece W, and the direction from rear to front is the sub-scanning direction (the transport direction F of the workpiece W, which intersects with the main scanning direction S).

[0095] The device frame 100 forms a framework for mounting various components of the inkjet printer 1000. The work transport unit 200 is a mechanism that intermittently feeds (transports) the work W so that the work W progresses in a transport direction F from rear to front in a printing area where inkjet printing processing is performed. The carriage 30 is equipped with an ink head 4, a pre-treatment liquid head 5, a post-treatment liquid head 6, and a sub-tank 70, and moves back and forth in a main scanning direction S (left and right direction) that intersects with the transport direction F of the work W during inkjet printing processing.

[0096] The device frame 100 includes a central frame 111, a right frame 112, and a left frame 113. The central frame 111 forms a framework for mounting various components of the inkjet printer 1000, and has a left-to-right width corresponding to the work transport unit 200. The right frame 112 and the left frame 113 are erected to the right and left, respectively, of the central frame 111. Between the right frame 112 and the left frame 113 is the printing area 12 where printing processing is performed on the work W.

[0097] The right frame 112 forms the maintenance area 13. The maintenance area 13 is an area where the carriage 30 is retracted when printing processing is not being performed. In the maintenance area 13, cleaning processing, purging processing, etc. are performed on the nozzles (ejection holes) of the ink heads 4, pre-treatment liquid head 5, and post-treatment liquid head 6. Caps are also fitted into the maintenance area 13. The left frame 113 forms a turn-back area 14 for the carriage 30. The turn-back area 14 is an area where the carriage 30 temporarily enters when it performs a main scan in the opposite direction after performing a main scan in the opposite direction across the printing area 12 from right to left during printing processing.

[0098] A carriage guide 15 for moving the carriage 30 back and forth in the left-right direction is attached to the upper side of the device frame 100. The carriage guide 15 is a flat plate-shaped member that is long in the left-right direction, and is disposed above the work transport unit 200. A timing belt 16 is attached to the carriage guide 15 so as to be able to move in a circular motion in the left-right direction (main scanning direction). The timing belt 16 is an endless belt that is driven to move in a circular motion in the left or right direction.

[0099] The carriage guide 15 is equipped with a pair of upper and lower guide rails 17 that extend parallel to the left and right and that support the carriage 30 in a state that allows it to move back and forth in the main scanning direction S. The carriage 30 is engaged with the guide rails 17. The carriage 30 is also fixed to a timing belt 16. As the timing belt 16 moves orbitally left or right, the carriage 30 moves left or right along the carriage guide 15 while being guided by the guide rails 17.

[0100] Next, a description will be given mainly with reference to Figure 4. The work transport section 200 includes a feed roller 21 that pays out the work W before printing, and a take-up roller 22 that takes up the work W after printing. The feed roller 21 is located at the rear lower part of the device frame 100, and is a take-up shaft for the feed roll WA, which is a roll of the work W before printing. The take-up roller 22 is located at the front lower part of the device frame 100, and is a take-up shaft for the take-up roll WB, which is a roll of the work W after the printing process. A first motor M1 is attached to the take-up roller 22, which drives the take-up roller 22 to rotate about its axis and perform the operation of winding up the work W.

[0101] The path between the delivery roller 21 and the take-up roller 22, which passes through the printing area 12, is the transport path for the workpiece W. Arranged on this transport path, in order from upstream, are a first tension roller 23, a work guide 24, a transport roller 25 and a pinch roller 26, a turn-back roller 27, and a second tension roller 28. The first tension roller 23 applies a predetermined tension to the workpiece W on the upstream side of the transport roller 25. The work guide 24 changes the transport direction of the workpiece W from upward to forward, allowing the workpiece W to enter the printing area 12.

[0102] The transport roller 25 is a roller that generates a transport force that intermittently feeds the workpiece W in the printing area 12. The transport roller 25 is driven to rotate around its axis by the second motor M2, and intermittently transports the workpiece W forward (predetermined transport direction F) so that the workpiece W passes through the printing area 12 (image forming position) facing the carriage 30. The pinch roller 26 is disposed opposite the transport roller 25 from above, and forms a transport nip portion with the transport roller 25.

[0103] The turn-back roller 27 changes the transport direction of the workpiece W that has passed through the printing area 12 from forward to downward, and guides the workpiece W after printing to the take-up roller 22. The second tension roller 28 applies a predetermined tension to the workpiece W downstream of the transport roller 25. A platen 29 is disposed below the transport path of the workpiece W in the printing area 12.

[0104] The carriage 30 is cantilevered by the guide rail 17 and moves back and forth in a main scanning direction S (left and right in FIGS. 3 and 4) that intersects with the transport direction F (orthogonal in FIGS. 3 and 4). The carriage 30 includes a carriage frame 30A, and an ink head 4, a pre-treatment liquid head 5, a post-treatment liquid head 6, and a sub-tank 70 that are mounted on the carriage frame 30A (see FIG. 3). The carriage frame 30A includes a head support frame 31 and a back frame 32.

[0105] The head support frame 31 is a horizontal plate that holds the ink heads 4, pre-treatment liquid head 5, and post-treatment liquid head 6 described above. The back frame 32 is a vertical plate that extends upward from the rear end edge of the head support frame 31. As described above, the timing belt 16 is fixed to the back frame 32. Furthermore, the guide rails 17 are engaged with the back frame 32. That is, in the example shown in FIG. 4, the back frame 32 is an engagement portion that is held in a cantilevered state by the guide rails 17. The head support frame 31 is a horizontal plate whose rear end side is supported in a cantilevered state by the guide rails 17 via the engagement portion.

[0106] The cantilevered state refers to a state in which the engagement portion (back frame 32), which is a portion of the carriage 30 that is held by the guide rail 17, which is a holding member, is present only on one side, either upstream or downstream, from the center of the carriage 30 in the transport direction F, and no other engagement portion is present on the side opposite to the side where the engagement portion is present. The engagement portion may also be located outside the range in which the ink heads 4 and the treatment heads are arranged in the transport direction F. That is, the engagement portion may be located only upstream or only downstream of the range in which the ink heads 4, the pre-treatment liquid heads 5, and the post-treatment liquid heads 6 are arranged in the transport direction F.

[0107] The carriage 30 will now be further described. Fig. 5 is an enlarged perspective view of the carriage shown in Fig. 3. Fig. 5 shows the transport direction F (sub-scanning direction) of the workpiece W and the main scanning direction S, which is the direction of movement of the carriage 30. Fig. 5 shows an example in which the carriage 30 is equipped with a plurality of ink heads 4 that eject ink for image formation onto the workpiece W, a pre-treatment liquid head 5 and a post-treatment liquid head 6 that eject non-color-forming treatment liquid, and a plurality of sub-tanks 70 that supply ink, pre-treatment liquid, and post-treatment liquid to these ink heads 4, pre-treatment liquid head 5, and post-treatment liquid head 6.

[0108] Each ink head 4 has a number of nozzles (ink ejection holes) that eject ink droplets using an ejection method such as a piezoelectric method using a piezoelectric element or a thermal method using a heating element, and ink passages that guide ink to the nozzles. The inks that can be used include those described in detail above. In the example shown in FIG. 5, the multiple ink heads 4 are capable of ejecting eight colors of ink. The ink heads 4 are mounted on the head support frame 31 of the carriage 30 so as to be aligned in two rows in the main scanning direction S. Each color ink head 4 has two heads.

[0109] In the example shown in FIG. 5, the ink heads 4 include a first upstream ink head 41A and a first downstream ink head 41B. These ink heads 4 eject, for example, yellow ink. The ink heads 4 also include a second upstream ink head 42A and a second downstream ink head 42B. These ink heads 4 eject, for example, magenta ink. Similarly, as shown in FIG. 5, two ink heads 4 that eject ink of the same color are arranged at positions shifted from each other in the transport direction F and the main scanning direction S. These two ink heads 4 form a group, and a total of eight groups of ink heads 4 (41A to 48A, 41B to 48B) eject inks of different colors.

[0110] The pre-treatment liquid head 5 and the post-treatment liquid head 6 are disposed at positions different from the ink heads 4 in the transport direction F. The pre-treatment liquid head 5 is disposed upstream of the ink heads 4 in the transport direction F. FIG. 5 shows an example in which one pre-treatment liquid head 5 is disposed near the left end of the array of ink heads 4. Similarly, the post-treatment liquid head 6 is disposed downstream of the ink heads 4 in the transport direction F. FIG. 5 shows an example in which one post-treatment liquid head 6 is disposed at the right end of the array of ink heads 4. In other embodiments, a plurality of pre-treatment liquid heads 5 or a plurality of post-treatment liquid heads 6 may be disposed.

[0111] A series of heads along the main scanning direction S, which are made up of the ink heads 4, pre-treatment liquid heads 5, and post-treatment liquid heads 6, will be referred to as a row of heads, or simply as a row. Also, a series of heads along the transport direction F, which are made up of the ink heads 4, pre-treatment liquid heads 5, and post-treatment liquid heads 6, will be referred to as a row of heads, or simply as a row.

[0112] The pretreatment liquid head 5 ejects a pretreatment liquid for performing a predetermined pretreatment on the workpiece W. The pretreatment liquid is ejected from the pretreatment liquid head 5 to a position on the workpiece W where ink has not yet been ejected from the ink head 4. The pretreatment liquid may be the same as that described above.

[0113] The post-treatment liquid head 6 ejects a post-treatment liquid for performing a predetermined post-treatment on the workpiece W to which ink has adhered. The post-treatment liquid is ejected from the post-treatment liquid head 6 onto the position of the workpiece W after the ink has been ejected from the ink head 4. The post-treatment liquid described above can be used as the post-treatment liquid. In this case, to produce the printed textile according to this embodiment, as described above, the ejection amount of the post-treatment liquid (the amount ejected per ejection and the total amount ejected) is adjusted to an appropriate amount so that a penetration gradient is formed in which the amount of silicone component decreases from the front side to the back side of the printed textile.

[0114] 3 to 5, the pretreatment liquid, ink, and posttreatment liquid are ejected in this order onto the workpiece W in the areas where colors are to be printed in accordance with the image. In this case, the ink may be of one color or multiple colors. In areas where colors are not to be printed, i.e., areas where ink is not to be ejected, the pretreatment liquid and posttreatment liquid are not basically ejected either.

[0115] 5, openings 31H are provided in the head support frame 31 at positions where the heads are arranged. The ink heads 4, the pre-treatment liquid heads 5, and the post-treatment liquid heads 6 are attached to the head support frame 31 so as to fit into the respective openings 31H. Nozzles arranged on the lower end surfaces of the heads (ink heads 4, pre-treatment liquid heads 5, and post-treatment liquid heads 6) are exposed from the respective openings 31H.

[0116] The plurality of sub-tanks 70 are supported by the carriage 30 above the respective heads (ink heads 4, pre-treatment liquid heads 5, and post-treatment liquid heads 6) via a holding frame (not shown). The plurality of sub-tanks 70 are provided corresponding to each of the ink heads 4, pre-treatment liquid heads 5, and post-treatment liquid heads 6. Ink or treatment liquid is supplied to each sub-tank 70 from a main tank 90 that contains ink and treatment liquid, and these are supplied to each head. Each sub-tank 70 and each head are connected by a pipe (not shown).

[0117] 5, the multiple sub-tanks 70 include a first supply sub-tank 71A to an eighth supply sub-tank 78A, a pre-processing supply sub-tank 7FA, and a post-processing supply sub-tank 7RA, which are arranged on the rear side along the main scanning direction S. Furthermore, the multiple sub-tanks 70 include a first recovery sub-tank 71B to an eighth recovery sub-tank 78B, a pre-processing recovery sub-tank 7FB, and a post-processing recovery sub-tank 7RB, which are arranged on the front side along the main scanning direction S.

[0118] In the example shown in FIG. 5, the first supply sub-tank 71A and the first recovery sub-tank 71B located on the far left side of the carriage 30 store, for example, yellow ink containing a pigment. In this case, the first supply sub-tank 71A supplies yellow ink to the first upstream ink head 41A and the first downstream ink head 41B (both of which are also referred to as supply destinations). Meanwhile, the first recovery sub-tank 71B stores yellow ink recovered from the first upstream ink head 41A and the first downstream ink head 41B. As described above, some of the yellow ink is ejected from the first upstream ink head 41A and the first downstream ink head 41B toward the workpiece W. Similarly, for example, the second supply sub-tank 72A supplies magenta ink to the second upstream ink head 42A and the second downstream ink head 42B. Meanwhile, the second recovery sub-tank 72B stores magenta ink recovered from the second upstream ink head 42A and the second downstream ink head 42B. The other sub-tanks, the third to eighth sub-tanks, have the same structure and function as those described above.

[0119] The pre-treatment supply sub-tank 7FA supplies the pre-treatment liquid to the pre-treatment liquid head 5, and the pre-treatment recovery sub-tank 7FB recovers the pre-treatment liquid from the pre-treatment liquid head 5. The post-treatment supply sub-tank 7RA supplies the post-treatment liquid to the post-treatment liquid head 6, and the post-treatment recovery sub-tank 7RB recovers the post-treatment liquid from the post-treatment liquid head 6.

[0120] 3 to 5 is an all-in-one printer in which three types of heads, the ink head 4, the pre-treatment liquid head 5, and the post-treatment liquid head 6, are mounted on a single carriage 30. With this inkjet printer 1000, the pre-treatment liquid ejection process and the post-treatment liquid ejection process can be carried out integrally in the printing process of inkjet printing onto fabric in digital textile printing, for example. This makes it possible to simplify the textile printing process and make the textile printing device more compact.

[0121] 3 to 5 performs printing on the workpiece W using a serial printing method. Specifically, if the workpiece W is wide, it is generally not possible to print on the workpiece W while continuously feeding it. The serial printing method is a printing method in which a carriage 30 carrying ink heads 4 of each color moves back and forth in the main scanning direction S, and the workpiece W is intermittently fed in the transport direction F, repeatedly.

[0122] The serial printing method will be described in detail. In the inkjet printer 1000 illustrated in FIGS. 3 to 5, a band-shaped image is printed while the carriage 30 moves in a forward direction, which is one of the main scanning directions S. The feeding of the workpiece W is stopped during this forward main scanning. After the band-shaped image is printed, the workpiece W is sent out in the transport direction F by a predetermined pitch. At this time, the carriage 30 waits in the return area 14 on the left end side. After the workpiece W is sent out, the carriage 30 returns in the return direction, opposite to the forward direction, as the timing belt 16 moves in reverse. At this time, the workpiece W is stationary. Then, as the carriage 30 moves in the return direction, the next band-shaped image is printed upstream of the band-shaped image printed during the forward movement. Similar operations are repeated thereafter.

[0123] Summary of this disclosure A printed item according to a first aspect of the present disclosure is a printed item in which a treatment agent containing a pigment, binder resin particles, and a silicone component is adhered to an object to be printed, The silicone component is present on both the front surface and the back surface of the print, and The amount of the silicone component is less on the back surface than on the front surface.

[0124] The print has good handle and rubfastness properties.

[0125] A printed item according to a second aspect of the present disclosure is a printed item according to the first aspect, wherein the ratio of the amount of the silicone component on the back surface to the amount of the silicone component on the front surface is 70% or less.

[0126] By having such a constitution, it is possible to improve the rub fastness, particularly wet rub fastness, of the printed product.

[0127] A printed item according to a third aspect of the present disclosure is a printed item according to the second aspect, wherein the ratio of the amount of the silicone component on the back surface to the amount of the silicone component on the front surface is greater than 15%.

[0128] By having such a constitution, the printed item can reliably have a good texture.

[0129] A printed item according to a fourth aspect of the present disclosure is a printed item according to the third aspect, wherein the ratio of the amount of the silicone component on the back surface to the amount of the silicone component on the front surface is 31% or more.

[0130] By having such a constitution, the printed item can more reliably have a good texture.

[0131] A printed item according to a fifth aspect of the present disclosure is a printed item according to the fourth aspect, wherein the ratio of the amount of the silicone component on the back surface to the amount of the silicone component on the front surface is 46% or more and 60% or less.

[0132] By having such a constitution, the printed item can more reliably have good texture and rub fastness properties (particularly wet rub fastness).

[0133] A printed material according to a sixth aspect of the present disclosure is a printed material according to any one of the first to fifth aspects, wherein the pigment is present on the front surface of the printed material and in an inner layer portion between the front surface and the back surface of the printed material.

[0134] By having such a configuration, the color of the image on the printed textile can be made vivid.

[0135] A printed item according to a seventh aspect of the present disclosure is the printed item according to any one of the first to sixth aspects, in which the pigment is not present on the back surface of the printed item.

[0136] Such a configuration can make the color of the image on the printed textile more vivid, and it is also expected that the texture on the back side of the printed textile can be improved.

[0137] A printed item according to an eighth aspect of the present disclosure is the printed item according to any one of the first to seventh aspects, in which the object to be printed is a polyester fabric.

[0138] It is expected that such a constitution will further ensure that the printed item has good texture and rub fastness properties.

[0139] A printed item according to a ninth aspect of the present disclosure is the printed item according to any one of the first to eighth aspects, and is an inkjet printed item.

[0140] By having such a constitution, it is possible to easily obtain a printed item having good texture and rub fastness properties. [Example]

[0141] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples in any way.

[0142] In this example, various evaluation prints were prepared by varying the ratio of the detected amount of Si on the back surface to the front surface of the print. Furthermore, the texture and rub fastness of each evaluation print were evaluated. Additionally, the cross sections of the evaluation prints were observed to confirm the location of the pigment, and the color development of the evaluation prints was also evaluated.

[0143] 1. Method for preparing printed items for evaluation The printed textiles for evaluation in each of the Examples and Comparative Examples were prepared by the following method.

[0144] Example 1 The printed textile for evaluation in Example 1 was produced by ejecting the pre-treatment liquid, ink (Black), and post-treatment liquid in that order onto the polyester tropical material to be printed using an inkjet printer. Below, the methods for preparing the pre-treatment liquid, ink, and post-treatment liquid, and the method for producing the printed textile for evaluation in Example 1 using these will be described.

[0145] [How to prepare pretreatment liquid] First, the adjusted cationic polymer solution to be contained in the pretreatment solution was prepared. A column was packed with 0.5 L of strongly basic ion exchange resin (OH type), and 1 L of "PAS-A-5" (manufactured by Nittobo Medical Co., Ltd.) was passed through at a flow rate of 50 mL / min to obtain the adjusted cationic polymer solution. "PAS-A-5" is a cationic polymer of quaternary ammonium salt (diallyldimethylammonium chloride-sulfur dioxide copolymer). The solids content of the obtained adjusted cationic polymer solution was 40%.

[0146] Next, 3 parts by mass (solid content) of the prepared cationic polymer solution, 2 parts by mass of succinic acid, 1 part by mass of a nonionic surfactant ("Surfynol 440" manufactured by Nissin Chemical Industry Co., Ltd.), 10 parts by mass of propylene glycol, and the remainder of the solution (adjusted to a total of 100 parts by mass) containing water were added and mixed. The mixture was then filtered using a 5 μm filter to obtain a pretreatment solution (pH 8.0, chloride ion concentration 4.5 g / L).

[0147] [How to make ink (black)] A 1-liter, three-necked flask equipped with a stirring blade was charged with 125 g of ion-exchanged water and 2 g of a nonionic surfactant (Nissin Chemical Industry Co., Ltd.'s "Surfynol (registered trademark) 440," content: acetylene glycol ethylene oxide adduct). While stirring the contents of the flask, 165 g of propylene glycol, 100 g of a black pigment dispersion (Sanyo Dye Co., Ltd.'s "AE2078F," content: CI Pigment Black 7, solids concentration: 20% by mass), and 108 g of a binder resin particle dispersion (Dai-ichi Kogyo Seiyaku Co., Ltd.'s "Superflex 470," content: polyurethane dispersion, solids concentration: 38% by mass) were added to the flask in this order. The contents of the flask were further stirred for 10 minutes to obtain an ink (Black).

[0148] [How to prepare post-processing liquid] First, the silicone emulsion to be contained in the post-treatment liquid was prepared. Specifically, 300 g of amino-modified silicone oil ("KF-864" manufactured by Shin-Etsu Chemical Co., Ltd., viscosity: 1,700 mm 2 A beaker was charged with 600 g of ion-exchanged water (H2O, specific gravity: 0.98 (25°C), functional group equivalent: 3,800 g / mol), 600 g of ion-exchanged water, and 100 g of aqueous hydrochloric acid solution (concentration: 1 mol / L). The contents of the beaker were then stirred at 10,000 rpm for 15 minutes using a homogenizer (IKA Corporation, Ultra Turrax T25) and allowed to stand for 30 minutes. The contents of the beaker were then filtered through a 120-mesh stainless steel filter to obtain a silicone emulsion.

[0149] Next, a post-treatment liquid was prepared using the silicone emulsion prepared as described above. Specifically, 30 g of the silicone emulsion was mixed with 35 g of ion-exchanged water and 35 g of propylene glycol to obtain a post-treatment liquid.

[0150] [Method for producing printed textiles for evaluation in Example 1] The subject of printing was polyester tropical fabric (manufactured by Shikisensha Co., Ltd., warp: 150 denier - 48 filament, weft: 150 denier - 48 filament, warp density: 76 threads / inch, weft density: 68 threads / inch, basis weight: 120 g / m 2 ) was used. A flatbed printer jig in which inkjet printheads (KJ4B manufactured by Kyocera Corporation) were arranged in the transport direction was used to produce the printed textile for evaluation. The first printhead was filled with the pre-treatment liquid prepared above. The second printhead was filled with the ink (black) prepared above. The third printhead was filled with the post-treatment liquid prepared above. Using the flatbed printer jig, the ejection amounts (total ejection amounts) of the pre-treatment liquid, ink (black) and post-treatment liquid were each 10 g / m 2 , 20g / m 2 , and 5 g / m 2 The ink was ejected from each head onto polyester tropical so that the ink droplets were 18 pL per ejection and 9 pL per ejection of each treatment liquid. These droplet sizes were used to eject the required number of times according to the total ejection volume. The ink and each treatment liquid were printed with a 1-second interval between them. The inkjet printing conditions were a fabric / head distance of 3 mm and a head temperature of 25°C. The subject to be printed was then heated in an oven at 160°C for 3 minutes to dry the ink and both treatment liquids, yielding a printed fabric for evaluation of Example 1.

[0151] Example 2 The discharge amount (total discharge amount) of the post-treatment liquid when producing the evaluation printed material was 20 g / m 2 A printed material for evaluation of Example 2 was prepared in the same manner as in Example 1, except that:

[0152] Example 3 The discharge amount (total discharge amount) of the post-treatment liquid when producing the evaluation printed material was 40 g / m 2 A printed material for evaluation of Example 3 was prepared in the same manner as in Example 1, except that:

[0153] Example 4 The subject of printing was cotton broadcloth (manufactured by Irosen Co., Ltd., size: A4, cotton count of warp and weft: 40 / 1, warp density: 130 threads / inch, weft density: 75 threads / inch, basis weight: 122 g / m 2 A printed fabric for evaluation of Example 4 was prepared in the same manner as in Example 1, except that the above-mentioned ink was used.

[0154] Example 5 A printed textile for evaluation of Example 5 was prepared in the same manner as in Example 1, except that an ink (yellow) prepared by the following method was used instead of the ink (black).

[0155] [How to make ink (Yellow)] A 1-liter, three-necked flask equipped with a stirring blade was charged with 110 g of ion-exchanged water and 2 g of a nonionic surfactant ("Surfynol (registered trademark) 440" manufactured by Nissin Chemical Industry Co., Ltd., content: acetylene glycol ethylene oxide adduct). While stirring the contents of the flask, 163 g of propylene glycol, 100 g of a yellow pigment dispersion ("AE2032F" manufactured by Sanyo Dishwashing Co., Ltd., content: CI Pigment Yellow 74, solids concentration: 20% by mass), and 125 g of a binder resin particle dispersion ("Superflex 420" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., content: polyurethane dispersion, solids concentration: 32% by mass) were added to the flask in this order. The contents of the flask were further stirred for 10 minutes to obtain an ink (Yellow).

[0156] Example 6 When preparing the printed fabric for evaluation, the post-treatment liquid was sprayed at a rate of 10 g / m 2 A printed textile for evaluation of Example 6 was prepared in the same manner as in Example 1, except that the dye was applied to the object to be printed in an amount (total amount applied) of 1000 ppm.

[0157] Example 7 A printed textile for evaluation of Example 7 was prepared in the same manner as in Example 1, except that an ink (cyan) prepared by the following method was used instead of the ink (black).

[0158] [Ink (cyan) preparation method] A 1-liter, three-necked flask equipped with a stirring blade was charged with 110 g of ion-exchanged water and 2 g of a nonionic surfactant (Surfynol® 440, manufactured by Nissin Chemical Industry Co., Ltd., content: acetylene glycol ethylene oxide adduct). While stirring the contents of the flask, 163 g of propylene glycol, 100 g of a blue pigment dispersion (BA2447F, manufactured by Sanyo Dishwashing Co., Ltd., content: CI Pigment Blue 15, solids concentration: 20% by mass), and 125 g of a binder resin particle dispersion (Superflex 420, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., content: polyurethane dispersion, solids concentration: 32% by mass) were added to the flask in this order. The contents of the flask were further stirred for 10 minutes to obtain an ink (cyan).

[0159] Example 8 A printed textile for evaluation of Example 8 was prepared in the same manner as in Example 1, except that an ink (magenta) prepared by the following method was used instead of the ink (black).

[0160] [Ink (Magenta) production method] A 1-liter, three-necked flask equipped with a stirring blade was charged with 110 g of ion-exchanged water and 2 g of a nonionic surfactant (Surfynol® 440, manufactured by Nissin Chemical Industry Co., Ltd., content: acetylene glycol ethylene oxide adduct). While stirring the contents of the flask, 163 g of propylene glycol, 100 g of a red pigment dispersion (AG2172F, manufactured by Sanyo Dishwashing Co., Ltd., content: CI Pigment Red 122, solids concentration: 20% by mass), and 125 g of a binder resin particle dispersion (Superflex 420, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., content: polyurethane dispersion, solids concentration: 32% by mass) were added to the flask in this order. The contents of the flask were further stirred for 10 minutes to obtain an ink (Magenta).

[0161] Example 9 The ejection amount (total ejection amount) of ink (black) when producing the evaluation printed material was 10 g / m 2 A printed fabric for evaluation of Example 9 was prepared in the same manner as in Example 1, except that:

[0162] Example 10 The discharge amount (total discharge amount) of the post-treatment liquid when producing the evaluation printed material was 10 g / m 2 A printed material for evaluation of Example 10 was prepared in the same manner as in Example 1, except that:

[0163] Example 11 The subject of printing was polyester satin fabric (Stretch Royal Satin manufactured by Uni Seni Co., Ltd., warp density: approximately 100 threads / inch (measured), weft density: approximately 80 threads / inch (measured), basis weight: approximately 100 g / m 2 (actual measurement)), the ejection amount (total ejection amount) of the ink (black) and post-treatment liquid when preparing the evaluation printed material was 40 g / m 2 and 10 g / m 2 A printed material for evaluation of Example 11 was prepared in the same manner as in Example 1, except that:

[0164] Example 12 The subject of printing was nylon taffeta fabric (R5050 manufactured by Uni Seni Co., Ltd., warp density: approximately 100 threads / inch (measured), weft density: approximately 80 threads / inch (measured), basis weight: approximately 70 g / m 2 A printed fabric for evaluation of Example 12 was prepared in the same manner as in Example 1, except that the ink composition (actual measurement) was used.

[0165] Example 13 The subject of printing was acetate satin fabric (KKF2660 Acetate Melon Vintage Satin manufactured by Uni Seni Co., Ltd., warp density: approximately 100 threads / inch (measured), weft density: approximately 80 threads / inch (measured), basis weight: approximately 120 g / m 2 A printed fabric for evaluation of Example 13 was prepared in the same manner as in Example 1, except that the ink composition (actual measurement) was used.

[0166] Example 14 The ejection amount (total ejection amount) of the ink (black) and post-treatment liquid when preparing the evaluation printed material was 40 g / m 2 and 10 g / m 2 A printed material for evaluation of Example 14 was prepared in the same manner as in Example 13, except that:

[0167] Example 15 The subject of printing was rayon sufmuslin fabric (manufactured by Shikisensha Co., Ltd., warp thread: 40 count - 1 thread, weft thread: 40 count - 1 thread, warp density: 87 threads / inch, weft density: 72 threads / inch, basis weight: 99 g / m 2 A printed item for evaluation of Example 15 was prepared in the same manner as in Example 1, except that the above-mentioned ink was used.

[0168] Example 16 The ejection amount (total ejection amount) of the ink (black) and post-treatment liquid when preparing the evaluation printed material was 40 g / m 2 and 10 g / m 2 A printed material for evaluation of Example 16 was prepared in the same manner as in Example 15, except that:

[0169] Example 17 The subject of printing was Tencel satin fabric (TN8811 manufactured by Uni Seni Co., Ltd., warp thread: 80 count - 1 thread, weft thread: 80 count - 1 thread, warp density: 210 threads / inch, weft density: 120 threads / inch, basis weight: approximately 100 g / m 2 A printed material for evaluation of Example 17 was prepared in the same manner as in Example 1, except that the ink composition (actual measurement) was used.

[0170] Example 18 The ejection amount (total ejection amount) of the ink (black) and post-treatment liquid when preparing the evaluation printed material was 40 g / m 2 and 10 g / m 2 A printed material for evaluation of Example 18 was prepared in the same manner as in Example 17, except that:

[0171] Example 19 The ejection amount (total ejection amount) of ink (black) when producing the evaluation printed material was 10 g / m 2 A printed material for evaluation of Example 19 was prepared in the same manner as in Example 4, except that:

[0172] Example 20 The discharge amount (total discharge amount) of the post-treatment liquid when producing the evaluation printed material was 10 g / m 2 A printed material for evaluation of Example 20 was prepared in the same manner as in Example 4, except that:

[0173] Example 21 The ejection amount (total ejection amount) of the ink (black) and post-treatment liquid when preparing the evaluation printed material was 40 g / m 2 and 10 g / m 2 A printed material for evaluation of Example 21 was prepared in the same manner as in Example 4, except that:

[0174] (Comparative Example 1) A printed textile for evaluation of Comparative Example 1 was prepared in the same manner as in Example 1, except that the post-treatment liquid was not ejected or applied during the preparation of the printed textile for evaluation.

[0175] (Comparative Example 2) When producing printed items, the post-treatment liquid is immersed at 100 g / m 2 The printed material of Comparative Example 2 was produced in the same manner as in Example 1, except that the dye was applied to the object to be printed in an amount (total amount applied) of 1000 ppm.

[0176] 2. Measurement of the amount of Si detected (Mass%) in quantitative analysis by EDX on the printed materials for evaluation in each Example and Comparative Example Using the prints for evaluation of each of the Examples and Comparative Examples prepared by the above-mentioned method, the amounts of silicone components (detected amount of Si) present on the front and back surfaces of the prints were measured.

[0177] [Method for measuring the amount of Si detected (Mass%) in quantitative analysis using EDX] First, the evaluation prints of each Example and Comparative Example were cut to an appropriate size. Au-Pd was vapor-deposited onto the cut prints at 10 mA for 60 seconds using an autofine coater ("JEC-3000FC," manufactured by JEOL Ltd.). Then, quantitative analysis was performed by EDX using a scanning electron microscope ("JSM-IT500," manufactured by JEOL Ltd.) under conditions of an acceleration voltage of 15 kV, a magnification of 200x, and a working distance of 10 mm. In the quantitative analysis by EDX, the mass % of Si was defined as the amount of Si detected, where the total of C, O, Si, and Au was taken as 100 mass %. The amount of Si detected (mass %) was measured on both the front and back surfaces of the evaluation prints.

[0178] The following Table 1 shows the amount of Si detected on the front surface, the amount of Si detected on the back surface, and the ratio of the amount of Si detected on the back surface to the amount of Si detected on the front surface for the printed evaluation materials of each Example and Comparative Example, along with the printing target, the ink ejection amount (total ejection amount) and its type, and the post-treatment liquid ejection amount (total ejection amount) or application amount (total application amount) and treatment method. The ratio of the amount of Si detected on the back surface to the amount of Si detected on the front surface was calculated by rounding off to one decimal place.

[0179] [Table 1]

[0180] In Table 1 above, the meanings of each term are as follows: "PET1" means polyester tropical fabric. "Cotton" means cotton broadcloth fabric. "PET2" means polyester satin fabric. "Ny" means nylon taffeta fabric. "Acetate" means acetate satin fabric. "Rayon" means rayon spun muslin fabric. "Lyocell" means Tencel satin fabric. Regarding the treatment method of the post-treatment liquid, "IJ" means inkjet printing method, "SP" means spray method, and "DP" means immersion method.

[0181] 3. Evaluation of the printed materials for evaluation in each of the Examples and Comparative Examples Using the prints for evaluation of each of the Examples and Comparative Examples produced by the above-mentioned method, the feel and rub fastness of the prints were evaluated.

[0182] [Evaluation method for texture (prevention of deterioration of tactile sensation)] An unused object to be printed was folded in half along the warp (lengthwise), and the distance (loop height) between the lower and upper fabrics at the fold was measured. The measured loop height of the unused object to be printed was taken as the loop height before printing. Next, the region of the prepared printed fabric for evaluation on which the solid image was formed was folded in half along the warp (lengthwise), and the loop height was measured. The measured loop height of the printed fabric for evaluation was taken as the loop height after printing. The change in loop height (unit: %) before and after printing was calculated according to the formula "change in loop height = 100 × loop height after printing / loop height before printing." A lower change in loop height means that the object to be printed does not harden or swell after printing, thereby suppressing deterioration in the feel of the printed fabric and indicating a good texture of the printed fabric. The texture of the printed textile (whether or not the deterioration of the feel was suppressed) was evaluated from the rate of change in loop height according to the following criteria. A rating of A or A' was considered to be pass, and a rating of B was considered to be fail. The measured rate of change in loop height and the evaluation results of texture are summarized in Table 2 below. Note that the ease with which the feel deteriorates due to printing varies depending on the type of textile to be printed, so the evaluation criteria for texture based on the rate of change in loop height were set as follows:

[0183] (Evaluation criteria for texture) Grade A: The rate of change in loop height is less than 130%. Evaluation A': The rate of change in loop height is 130%. Rating B: The rate of change in loop height exceeds 130%.

[0184] [Evaluation method for friction fastness] The solid image formed on the evaluation print was rubbed with a white cotton cloth according to the dry and wet tests using the Type II Rub Tester (Gakushin type) method described in JIS L-0849:2013 (Testing Methods for Color Fastness to Rubbing). The degree of discoloration of the white cotton cloth after rubbing was evaluated in accordance with the "Criteria for Judging Discoloration and Fading" described in Clause 10 (Judgment of Color Fastness) of JIS L-0801:2011 (General Rules for Testing Methods for Color Fastness). The degree of discoloration of the white cotton cloth after rubbing was evaluated on a nine-point scale (Grade 1, Grade 1-2, Grade 2, Grade 2-3, Grade 3, Grade 3-4, Grade 4, Grade 4-5, and Grade 5, in descending order of staining). The lower the degree of discoloration of the white cotton cloth after rubbing (closer to Grade 5), the better the rub fastness. The degree of discoloration of the white cotton cloth after rubbing was evaluated according to the following criteria: dry rub fastness and wet rub fastness. The results of the dry test were taken as the dry friction fastness, and the results of the wet test were taken as the wet friction fastness. A sample was deemed to have passed if there was no "B" in the evaluation results for both dry and wet friction fastness, and was deemed to have failed if there was at least one "B" in the evaluation results for both dry and wet friction fastness. The determined friction fastnesses and their evaluation results are summarized in Table 2 below.

[0185] (Evaluation criteria for dry rub fastness) Evaluation A: Dry rub fastness is grade 3 or higher. Evaluation B: The dry rub fastness is less than grade 3.

[0186] (Evaluation criteria for wet friction fastness) Evaluation A: Wet rubbing fastness is grade 2 or higher. Evaluation A': Wet rubbing fastness is grade 1-2. Evaluation B: Wet rubbing fastness is less than grade 1-2.

[0187] [Table 2]

[0188] [Consideration] First, as a premise, Tables 1 and 2 above show that the Si detection ratio on the back surface of a printed textile relative to the front surface can vary depending not only on factors such as the post-treatment liquid ejection amount (total ejection amount), application amount (total application amount), and coating amount (total application amount), but also on factors such as the type of textile to be printed, the ink ejection amount (total ejection amount), and the type of ink. For example, in Example 4, a printed textile for evaluation was prepared using the same method as in Example 1 except for the textile to be printed used, but the Si detection ratio on the back surface of the printed textile for evaluation was significantly different from the front surface. From these results, it is expected that the Si detection ratio for each textile to be printed will also vary depending on the droplet size of the ink and post-treatment liquid (or pre-treatment liquid, ink, and post-treatment liquid), the number of ejections, the ejection interval between these liquids, and the specific ejection, application, or coating method of these liquids. This is thought to be because the droplet size, number of ejections, ejection intervals, etc. affect the degree of penetration into the fabric differently depending on the type of object to be printed.

[0189] As shown in Tables 1 and 2, in Examples 1 to 21, in which the amount of Si detected on the back surface of the evaluation printed material (the amount of silicone component on the back surface) was smaller than the amount of Si detected on the front surface (the amount of silicone component on the front surface), the printed material produced had good texture and rub fastness properties. In particular, in Examples 1 to 2, 4 to 16, and 18 to 21, in which the ratio of Si detected on the back surface to the front surface of the evaluation printed material was 70% or less, the rub fastness of the printed material, especially wet rub fastness, was better.

[0190] Furthermore, when the Si detection ratio of the back surface to the front surface of the evaluation printed textile was more than 15%, the texture of the printed textile was better. Furthermore, when the Si detection ratio of the back surface to the front surface of the evaluation printed textile was preferably about 31% to 60%, more preferably about 46% to 60%, both the texture and rub fastness properties (particularly wet rub fastness) of the printed textile generally tended to be better. However, the tactile feel of cotton broadcloth and the like is easily reduced by printing, and the rate of change in loop height tended to be slightly greater than when other types of textile were used for printing.

[0191] On the other hand, the print for evaluation in Comparative Example 1 was not treated with a post-treatment liquid, and therefore the texture of the print was significantly inferior. The print for evaluation in Comparative Example 2 was inferior in dry rub fastness. This is thought to be because the amount of silicone component on the back surface was greater than the amount of silicone component on the front surface, and therefore the rub resistance of the image formed on the front side of the print was reduced.

[0192] 4. Confirmation of the location of pigments in the printed textiles for evaluation in the examples and evaluation of color development The location of the pigment in the printed textile was confirmed using the printed textile for evaluation of Example 1 prepared by the above-mentioned method, and then the color development properties of the printed textiles for evaluation of Examples 1, 4, and 5 prepared by the above-mentioned method were evaluated.

[0193] [Method for checking pigment locations and results] The location of the pigment was confirmed by the following method. First, the surface of the printed textile for evaluation of Example 1 prepared was fixed with Damplon Tape No. 357-50™ manufactured by Nitto Denko Corporation, and a cross-sectional sample of a 1 mm image-formed region was cut out using a high-stainless steel double-edged blade manufactured by Feather Corporation. Next, the cross-sectional sample of the image-formed region of the cut-out printed textile for evaluation was visually observed using an optical microscope (Keyence Corporation, "VHX-8000", magnification: 100x). As a result, the pigment was confirmed only on the front surface and in the inner layer portion of the printed textile.

[0194] [Color development evaluation method] The color development was evaluated using the evaluation printed textiles of Examples 1, 4, and 5. Specifically, the evaluation was carried out by measuring the image density (OD) of the evaluation printed textiles using a fluorescence spectrophotometer FD-5 (manufactured by Konica Minolta, Inc.). The evaluation criteria were as follows. The evaluation results are summarized in Table 3 below. Evaluation A (good color development): Image density (OD) is 1.25 or higher Grade B (poor color development): Image density (OD) is less than 1.25

[0195] [Table 3]

[0196] [Consideration] As shown in Table 3 above, the image density (OD) of the evaluation printed material of Example 1 was 1.28, and the evaluation result of color development was good. These results demonstrate that the presence of pigment only on the front surface and the inner layer of the printed material results in vivid image color development. The evaluation printed material of Example 4, which was printed on cotton broadcloth, also had an image density (OD) of 1.30, and the evaluation result of color development was good. Furthermore, the evaluation printed material of Example 5, which was printed using yellow ink, also had an image density (OD) of 1.25, and the evaluation result of color development was good.

[0197] This application is based on Japanese Patent Application No. 2023-093424 filed on June 6, 2023 and International Application No. PCT / JP2023 / 046879 filed on December 27, 2023, the contents of which are incorporated herein by reference.

[0198] The embodiments and examples disclosed herein should be understood to be illustrative in all respects and not restrictive. That is, the scope of the present disclosure includes at least all modifications within the meaning and scope equivalent to the claims. Furthermore, although the comparative examples were inferior in relative evaluation to the examples, this does not mean that the implementation content of the comparative examples themselves is excluded or abandoned. [Industrial Applicability]

[0199] According to the present disclosure, it is possible to obtain a printed item having good texture and rub fastness properties. [Explanation of symbols]

[0200] 10 Printed material, 10Sf Front surface of printed material, 10Sb Back surface of printed material, 10M Inner layer of printed material 1 pigment 2. Binder resin particles 3 Silicone ingredients 4 ink head, 4a first ink head, 4b second ink head, 4c third ink head, 4d fourth ink head 5 Pre-treatment liquid head 6 Post-treatment liquid head 7 Mounting table 20 Inkjet printing equipment (part) P Printing target 1000 inkjet printers 100 Equipment Frame 111 Center Frame 112 Right Frame 113 Left Frame 12 Printing Area 13 Maintenance Area 14 Turning Area 15 Carriage guide 16 Timing belt 17 Guide rail 200 Work transport section 21 Feed roller 22 Winding roller 23 First tension roller 24 Work Guide 25 Transport roller 26 Pinch Roller 27 Folding roller 28 Second tension roller 29 Platen 30 Carriage 30A Carriage Frame 31 Head support frame 31H opening 32 Back Frame 41A first upstream ink head, 41B first downstream ink head, 42A second upstream ink head, 42B second downstream ink head 70 Subtank 71A 1st supply sub-tank (supply tank), 71B 1st recovery sub-tank (recovery tank) 72A Second supply sub-tank, 72B Second recovery sub-tank 7FA pre-treatment supply sub-tank, 7FB pre-treatment recovery sub-tank 7RA post-treatment supply sub-tank, 7RB post-treatment collection sub-tank

Claims

1. A printed item in which a treatment agent containing a pigment, binder resin particles, and a silicone component is adhered to an object to be printed, The silicone component is present on both the front surface and the back surface of the print, and The amount of the silicone component is smaller on the back surface than on the front surface.

2. 2. The printed item according to claim 1, wherein the ratio of the amount of the silicone component on the back surface to the amount of the silicone component on the front surface is 70% or less.

3. The printed product according to claim 2, wherein the ratio of the amount of the silicone component on the back surface to the amount of the silicone component on the front surface is more than 15%.

4. The printed item according to claim 3 , wherein the ratio of the amount of the silicone component on the back surface to the amount of the silicone component on the front surface is 31% or more.

5. The printed item according to claim 4, wherein the ratio of the amount of the silicone component on the back surface to the amount of the silicone component on the front surface is 46% or more and 60% or less.

6. The printed textile according to any one of claims 1 to 5, wherein the pigment is present on the front surface of the printed textile and in an inner layer portion between the front surface and the back surface of the printed textile.

7. The print according to any one of claims 1 to 6, wherein the pigment is not present on the back surface of the print.

8. The printed item according to any one of claims 1 to 7, wherein the object to be printed is a polyester fabric.

9. The printed material according to any one of claims 1 to 8, which is an inkjet printed material.

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