Image formation method

Abstract

To provide an image formation method which enables utilization of existing equipment, causes no degradation in texture or no occurrence of bleeding, and is capable of preventing stickiness in a napped fibrous substrate.SOLUTION: An image formation method includes: a first step of imparting, by an inkjet process, an ink comprising a pigment, a water-dispersible resin, and water, and a first treatment liquid comprising a coagulant for aggregating the pigment or the water-dispersible resin and water, onto a napped fibrous substrate having napped fibers; a second step of drying the fibrous substrate to which the ink and the first treatment liquid have been imparted; and a third step of immersing the dried fibrous substrate in a second treatment liquid comprising a silicone-based resin and water.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an image forming method.

Background Art

[0002] In recent years, as a printing and dyeing method, inkjet printing and dyeing, which can perform image formation on a fabric by an inkjet method, has been widely performed because it can dye in a short time and has high production efficiency.

[0003] As the ink used in inkjet printing and dyeing, dye ink has been the mainstream, but the use of pigment ink, which can omit post-treatment such as a cleaning process for washing away undissolved or unreacted dyes, has been studied.

[0004] As for the fabric, there is also a fiber substrate whose surface fluff (raised hair) is increased by raising treatment or the like, and the increased fluff makes the touch softer and improves the texture.

[0005] On the other hand, when inkjet printing and dyeing is performed on such a fiber substrate having fluff using pigment ink, a part of the ink droplets ejected from the inkjet head may not reach the surface of the fiber substrate and adhere to the fluff on the raised surface like a "pool of ink", forming an "ink pool". If the ink pool is dried and solidified as it is, it will cause stickiness and reduce the rub resistance.

[0006] As a method for suppressing such a reduction in rub resistance, Patent Document 1 proposes a method of applying a large amount of clear ink to wash away the ink pool without drying after applying the ink by inkjet. Patent Document 2 proposes a method of removing the ink pool with an ink removing member.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] By the way, in inkjet printing, from the viewpoint of enhancing color development and rubbing resistance, a pigment ink and a treatment liquid containing a flocculant for aggregating the pigments and binder resins contained in the pigment ink may be used in combination.

[0009] However, when ink and a treatment liquid are ejected by inkjet onto a fibrous substrate having raised fibers, a part of the ink droplets does not reach the surface of the fibrous substrate body, and since the treatment liquid and the ink are likely to combine on the raised fibers, ink stains are more likely to adhere to the raised fibers. As a result, stickiness is more likely to occur significantly. In particular, when a water-dispersible resin having a low Tg is used as the water-dispersible resin of the ink in order to improve the texture, the stickiness becomes even more significant.

[0010] On the other hand, if a large amount of clear ink is applied immediately after applying the ink as in Patent Document 1 to wash away the ink stains to the root part of the raised fibers, since the solid content such as the ink is likely to stick to the surface of the fibrous substrate, the texture is likely to deteriorate. In addition, since the clear ink is applied without drying the ink, bleeding is likely to occur. Further, there is also a method of removing the ink stains with an ink-removing member as in Patent Document 2, but the device configuration is likely to become complicated.

[0011] On the other hand, if the treatment liquid or the ink is applied not by inkjet but by dipping treatment or coating, stains are less likely to be formed. However, since the amount of the treatment liquid or the ink applied increases, the fibrous substrate is likely to become hard and the texture is likely to be impaired.

[0012] The present invention has been made in view of the above problems, and an object thereof is to provide an image forming method that can use existing equipment and suppress the stickiness of a raised fibrous substrate without causing a deterioration in texture or bleeding.

Means for Solving the Problem

[0013] The present invention relates to the following image forming method.

[0014] [1] A first step of applying, by an inkjet method, an ink containing a pigment, a water-dispersible resin, and water, and a first treatment liquid containing a flocculant for aggregating the pigment or the water-dispersible resin and water, onto a pile fiber substrate having pile; a second step of drying the pile fiber substrate to which the first treatment liquid and the ink have been applied; and a third step of immersing the dried pile fiber substrate in a second treatment liquid containing a silicone-based resin and water. An image forming method. [2] The image forming method according to [1], wherein the flocculant contains a resin having a cationic group. [3] The image forming method according to [1] or [2], wherein the water-dispersible resin contains a water-dispersible resin having an anionic group. [4] The image forming method according to any one of [1] to [3], wherein the glass transition temperature of the water-dispersible resin is 0 °C or lower. [5] The image forming method according to any one of [1] to [4], wherein the water-dispersible resin contains a urethane resin. [6] The image forming method according to any one of [1] to [5], wherein the silicone-based resin is a water-dispersible silicone-based resin. [7] The image forming method according to [6], wherein the water-dispersible silicone-based resin contains a copolymer containing a structural unit derived from a polyorganosiloxane having a radically polymerizable group and a structural unit derived from a (meth)acrylate ester. [8] The image forming method according to any one of [6] or [7], wherein the glass transition temperature of the water-dispersible silicone-based resin is 30 °C or higher and 120 °C or lower. [9] The image forming method according to any one of [1] to [8], wherein the first treatment liquid and the ink each further contain a glycol-based solvent having a boiling point of 180 °C or higher.

[10] The image forming method according to any one of [1] to [9], wherein the length of the pile of the pile fiber substrate is 200 μm or more and 1000 μm or less.

Advantages of the Invention

[0015] According to the present invention, it is possible to provide an image forming method that can use existing equipment, suppress stickiness of a fluffed fiber substrate without causing a decrease in texture or bleeding.

Embodiments for Carrying Out the Invention

[0016] As described above, when an ink containing a water-dispersible resin and a treatment liquid containing a flocculant are ejected by inkjet onto a fiber substrate having raised hairs, a part of the ink droplets does not reach the surface of the fiber substrate body, and it is easy for the treatment liquid and the ink to combine on the raised hairs. Therefore, "ink pools" are more likely to adhere to the raised hairs, and stickiness becomes more prominent.

[0017] In contrast, in one embodiment of the present invention, 1) a first step of applying, by inkjet, a first treatment liquid containing a flocculant and water, and an ink containing a pigment, an aqueous dispersion resin, and water, to a fiber substrate having raised hairs; 2) a second step of drying the fiber substrate to which the ink or the like has been applied; and 3) a third step of immersing the dried fiber substrate in a second treatment liquid containing a silicone-based resin and water are performed.

[0018] In this way, the image formation having raised hairs is immersed in a second treatment liquid containing a silicone-based resin (third step). Thereby, it is possible to suppress the stickiness caused by ink pools adhering to the raised hairs. In addition, since the first treatment liquid is applied by inkjet (first step), the amount applied can be reduced compared to the case of applying by immersion treatment or coating, etc., so the texture is less likely to be impaired. Further, since a drying step is performed before immersion treatment with the second treatment liquid (second step), bleeding of the ink can be suppressed. Thereby, even when using existing equipment, it is possible to suppress the stickiness of the fluffed fiber substrate without causing a decrease in texture or bleeding.

[0019] Hereinafter, an image forming method according to an embodiment of the present invention will be described.

[0020] 1. Image forming method The image forming method according to an embodiment of the present invention includes a first step of applying a first treatment liquid and ink to a fiber substrate having raised hairs by an inkjet method, a second step of drying the fiber substrate to which the first treatment liquid and the ink have been applied, and a third step of immersing the dried fiber substrate in a second treatment liquid containing a silicone-based resin and water.

[0021] 1-1. First step The first treatment liquid and the ink are applied to the raised hair surface of the raised hair fiber substrate by an inkjet method.

[0022] (Raised hair fiber substrate) The raised hair fiber substrate is a fiber substrate having raised hairs, and has a fiber substrate and raised hairs (fiber fuzz) formed on its surface.

[0023] The fiber substrate includes woven fabrics, knitted fabrics, and non-woven fabrics of natural fibers such as cotton (cellulose fibers), hemp, wool, and silk; chemical fibers such as rayon, vinylon, nylon, acrylic, polyurethane, polyester, or acetate; or blended fibers thereof. Among them, from the viewpoints of durability, heat resistance, and light resistance, synthetic fibers are preferred as the fiber material, polyester fibers are more preferred, and polyethylene terephthalate fibers are particularly preferred.

[0024] The raised hairs are the fibers constituting the fiber substrate. The raised hairs include not only the fiber fuzz increased by raising on the surface of the fiber substrate but also the fiber fuzz naturally generated by weaving or the like when the fiber substrate is manufactured.

[0025] The length of the raised hairs is not particularly limited, but can be, for example, 200 to 1000 μm. When the length of the raised hairs is 200 μm or more, stickiness due to ink droplets is more easily felt. Also, when the length of the raised hairs is 1000 μm or less, it is possible to make it less likely to come into contact with the ejection surface of the inkjet head.

[0026] The density of the raised hairs is also not particularly limited. The density of the raised hairs is, for example, 100 hairs / cm 2 or more, or 100 to 400 hairs / cm 2If it is so, it becomes easier to feel stickiness due to ink puddles.

[0027] The thickness of the raised fiber base material is not particularly limited, but for example, it is preferably 50 μm or more and 1500 μm or less, and more preferably 60 μm or more and 200 μm or less. When the thickness of the raised fiber base material is at least the lower limit value, the wear resistance becomes better. When the thickness of the raised fiber base material is at most the upper limit value, the texture becomes better.

[0028] The thickness of the raised fiber base material is the thickness of the raised fiber base material before applying the treatment liquid or ink, but the thickness of the raised fiber base material after applying the treatment liquid or ink may also be within the same range.

[0029] The thickness of the raised fiber base material is a value measured using a constant-pressure thickness gauge (for example, Ozaki Seisakusho Co., Ltd.: Peacock Dial Gauge H-30) in accordance with JIS L1096 8.4A method (JIS method).

[0030] (Application of the first treatment liquid and ink) Next, the first treatment liquid and ink are applied to the raised surface of the raised fiber base material by an inkjet method.

[0031] As described later, the ink contains a pigment, a water-dispersible resin, and water. The first treatment liquid contains a flocculant that aggregates the above-described pigment and water-dispersible resin, and water. After applying the first treatment liquid, the ink may be applied, or after applying the ink, the first treatment liquid may be applied, or the first treatment liquid and the ink may be applied simultaneously. In the present embodiment, from the viewpoint of making it easier for the pigment in the ink to stay on the raised surface of the raised fiber base material, it is preferable to apply the ink after applying the first treatment liquid. By applying the first treatment liquid, a flocculant can be adhered to the raised hairs, so that the pigment and water-dispersible resin of the ink can be easily aggregated on the raised hairs. The configurations of the first treatment liquid and the ink will be described in detail later.

[0032] In addition, as the pilosebaceous fiber substrate, a flocculant may be pre - attached. In that case, in this step, only the ink may be applied without applying the first treatment liquid.

[0033] The application amount of the first treatment liquid is preferably an amount such that the adhesion amount of the flocculant is, for example, 1 - 50.0 g / m 2 and can be, for example, 5 - 30 g / m 2 Similarly, the application amount of the ink can be, for example, 1 - 50 g / m 2 In the present specification, the application amount means the amount including the solvent.

[0034] 1 - 2. Second step Next, the solvent component is removed from the first treatment liquid and the ink applied to the pilosebaceous fiber substrate, and it is dried. Thereby, even when immersed in the second treatment liquid containing the silicone - based resin in the third step described later, bleeding of the ink can be suppressed.

[0035] For example, it is preferable to dry until the remaining amount of the volatile component of the applied ink per unit area of the image forming region becomes 15 mass% or less.

[0036] The drying method is not particularly limited, and it may be a method of drying by blowing air, or a method of heat - drying by warm air, a heater, a heat roller, etc.

[0037] The drying temperature is not particularly limited as long as it can remove the solvent in the ink and the first treatment liquid to a certain extent or more, and can be, for example, 100 - 200 °C, preferably 130 - 180 °C. The drying time depends on the drying temperature, but can be, for example, 1 - 10 minutes.

[0038] 1 - 3. Third step Next, the erected fiber substrate to which the first treatment liquid and the ink have been applied is immersed in a second treatment liquid containing a silicone-based resin and water. As a result, the surface of the ink droplet adhering to the erected hair can be coated with the silicone-based resin, so that stickiness can be suppressed. The composition of the second treatment liquid will be described in detail later.

[0039] The content of the silicone-based resin in the second treatment liquid used for the immersion treatment is not particularly limited, but is preferably 2% by mass or more and 6% by mass or less with respect to the second treatment liquid. When the above content is 2% by mass or more, the silicone-based resin can coat the surface of the ink droplet in a shorter time, so that stickiness is more easily suppressed. When the above content is 6% by mass or less, it is possible to further suppress a decrease in texture due to an excessive adhesion amount of the silicone-based resin. From the same viewpoint, the above content is more preferably 3% by mass or more and 5% by mass or less.

[0040] The temperature of the second treatment liquid (immersion temperature) during the immersion treatment is not particularly limited and can be 10 to 40°C. The immersion time may be such that the surface of the ink droplet can be coated with the silicone-based resin, and can be, for example, 10 to 300 seconds.

[0041] The application amount of the second treatment liquid is such that the adhesion amount of the silicone-based resin is preferably 1 g / m 2 or more and 8 g / m 2 or less, more preferably 2 g / m 2 or more and 6 g / m 2 or less. When the adhesion amount of the silicone-based resin is within the above range, it is possible to further suppress stickiness while maintaining the texture of the erected fiber substrate better.

[0042] Next, it is preferable to dry the erected fiber substrate immersed in the second treatment liquid. The drying method can be the same as above.

[0043] 1-4. Other Processes The image forming method according to this embodiment may further include other steps as necessary. For example, in the first step, after applying ink, a third treatment liquid may be further applied.

[0044] The third treatment liquid contains a resin having a cationic group or an anionic group, water, and a water-soluble organic solvent. As the resin having a cationic group, the same resin as the resin having a cationic group contained in the first treatment liquid described later can be used. As the resin having an anionic group, the same resin as the water-dispersible resin having an anionic group contained in the ink described later can be used. The water-soluble organic solvent can also be the same as the water-soluble organic solvent contained in the first treatment liquid described later.

[0045] 2. First treatment liquid, ink, second treatment liquid Hereinafter, the first treatment liquid, ink, and second treatment liquid used in the above image forming method will be described.

[0046] 2-1. First treatment liquid The first treatment liquid contains a flocculant and water.

[0047] The flocculant may be any substance that interacts with the pigment (pigment dispersion containing a pigment and a pigment dispersant) or the water-dispersible resin contained in the ink to flocculate them. The flocculant may flocculate by utilizing a change in pH or by utilizing an electrical action.

[0048] Examples of the flocculant that flocculates by a change in pH include organic acids. The organic acids include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and hexanoic acid, and hydroxy acids such as lactic acid, malic acid, and citric acid, as carboxylic acids having 6 or less carbon atoms.

[0049] Examples of the flocculant that flocculates by an electrical action include polyvalent metal salts, and compounds having a cationic group or an anionic group. For example, when the pigment dispersant contained in the ink is anionic, the flocculant preferably contains a polyvalent metal salt or a compound having a cationic group.

[0050] The polyvalent metal salt can be a water-soluble compound having a polyvalent metal ion of divalent or higher and an anion that binds to it. Examples of polyvalent metal ions include divalent metal ions such as Ca 2+ , Cu 2+ , Ni 2+ , Mg 2+ , Zn 2+ , Ba 2+ ; trivalent metal ions such as Al 3+ , Fe 3+ , Cr 3+ . Examples of anions include Cl - , I - , Br - , SO4 2- , ClO3 - , NO3 - , and HCOO - , CH3COO - . Among them, calcium salts and magnesium salts are preferred, and calcium nitrate and calcium chloride are preferred.

[0051] Examples of the cationic group in the compound having a cationic group include a secondary amino group, a tertiary amino group, a quaternary ammonium base, etc. Examples of the compound having a cationic group include a resin having a cationic group and a cationic surfactant, and preferably a resin having a cationic group.

[0052] Examples of the resin having a cationic group include a cationic urethane resin, a cationic olefin resin, and a cationic alkylamine resin. Examples of commercially available products include MPT-60 (manufactured by Mitsubishi Pencil Co., Ltd.), Unisense KHE100L (manufactured by Senka Corporation), and MZ477 (manufactured by Takamatsu Oil & Fat Co., Ltd., urethane resin). Among them, from the viewpoint of making the pigment dispersion and the water-dispersible resin in the ink more likely to aggregate, the cationic alkylamine resins MPT-60 and Unisense KHE100L (manufactured by Senka Corporation) are preferred.

[0053] The content of the flocculant preferably is 1% by mass or more and 20% by mass or less, although it depends on the type thereof, for example, with respect to the first treatment liquid. When the content of the flocculant is 1% by mass or more, a sufficient amount can be adhered when applied by inkjet, so that the aggregation of the ink components can be more easily promoted. When the content of the flocculant is 20% by mass or less, the injectability becomes good.

[0054] The first treatment liquid preferably further contains a water-soluble organic solvent. Thereby, the ejection stability by inkjet can be further enhanced.

[0055] The water-soluble organic solvent is not particularly limited as long as it is compatible with water. Examples thereof include polyhydric alcohols (e.g., dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol; trihydric or higher alcohols such as glycerin, trimethylolpropane, hexanetriol); polyhydric alcohol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether); monohydric alcohols (e.g., methanol, ethanol, propanol, pentanol, hexanol, cyclohexanol, benzyl alcohol); amines (e.g., ethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine); amides (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide); heterocyclics (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (e.g., dimethyl sulfoxide); and sulfones (e.g., sulfolane).

[0056] From the perspective of further enhancing the ejection stability by inkjet, the water-soluble organic solvent preferably contains a water-soluble organic solvent having a boiling point of 180°C or higher, preferably 190°C or higher, more preferably 200°C or higher. Examples of water-soluble organic solvents having a boiling point of 180°C or higher include glycol solvents such as ethylene glycol (boiling point 197°C), propylene glycol (boiling point 188°C), 1,3-butanediol (boiling point 208°C), 1,6-hexanediol (boiling point 223°C), and polypropylene glycol; and alcohol solvents with a trivalent or higher valence such as glycerin (boiling point 290°C) and trimethylolpropane (boiling point 295°C).

[0057] The content of the water-soluble organic solvent is preferably, for example, 10% by mass or more and 65% by mass or less, more preferably 20% by mass or more and 45% by mass or less, based on the first treatment liquid.

[0058] The content of water is 30% by mass or more and 85% by mass or less, preferably 50% by mass or more and 75% by mass or less, based on the first treatment liquid.

[0059] The first treatment liquid may further contain a surfactant, a pH adjuster, a preservative, etc., as necessary.

[0060] The surfactant can lower the surface tension of the first treatment liquid and enhance the wettability with respect to the lint fiber substrate. The type of surfactant is not particularly limited, and examples thereof can be acetylene glycol-based surfactants, silicone-based surfactants, fluorine-based surfactants, etc.

[0061] Examples of the pH adjuster include citric acid, sodium citrate, hydrochloric acid, sodium hydroxide, etc.

[0062] Examples of the preservative include aromatic halogen compounds (e.g., Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (e.g., PROXEL GXL), etc.

[0063] Further, the first treatment liquid preferably does not substantially contain color materials such as pigments. "Not substantially contain" means that it is 0.1% by mass or less, preferably 0% by mass, with respect to the first treatment liquid.

[0064] 2-2. Ink The above ink contains a pigment, a water-dispersible resin, and water.

[0065] 2-2-1. Pigment The pigment is not particularly limited, and can be, for example, an organic pigment or an inorganic pigment with the following numbers described in the Color Index.

[0066] Examples of orange pigments include C.I.Pigment Orange 31 and 43.

[0067] Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36.

[0068] Examples of blue or cyan pigments include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60.

[0069] Examples of green pigments or yellow pigments include Pigment Green 7, 26, 36, 50. Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 15, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 128, 137, 138, 139, 151, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193, 213.

[0070] Examples of black pigments include Pigment Black 7, 28, 26.

[0071] Examples of white pigments include titanium dioxide and the like.

[0072] From the viewpoint of enhancing the dispersibility in the ink, it is preferable that the pigment is further dispersed with a pigment dispersant. The pigment dispersant will be described later.

[0073] Also, the pigment may be a self-dispersible pigment. A self-dispersible pigment is one in which the surface of the pigment particles is modified with a group having a hydrophilic group, and has pigment particles and a hydrophilic group bonded to the surface thereof.

[0074] Examples of the hydrophilic group include a carboxyl group, a sulfonic acid group, and a phosphorus-containing group. Examples of the phosphorus-containing group include a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a phosphite group, and a phosphate group.

[0075] Examples of commercially available self-dispersible pigments include Cabot Cab-0-Jet (registered trademark) 200K, 250C, 260M, 270V (sulfonic acid group-containing self-dispersible pigments), Cab-0-Jet (registered trademark) 300K (carboxylic acid group-containing self-dispersible pigments), Cab-0-Jet (registered trademark) 400K, 450C, 465M, 470V, 480V (phosphoric acid group-containing self-dispersible pigments).

[0076] The content of the pigment is not particularly limited. However, from the perspective of easily adjusting the viscosity of the ink within the above range and enabling the formation of high-concentration images, it is preferably 0.3% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 6% by mass or less, based on the ink. When the content of the pigment is at least the lower limit value, the color of the image is more likely to be vivid. When the content of the pigment is at most the upper limit value, it is easier to further suppress the increase in the viscosity of the ink, and the ejection stability is less likely to be impaired.

[0077] 2-2-2. Water-dispersible resin The water-dispersible resin functions as a binder resin for fixing the pigment to the flocked fiber substrate. The water-dispersible resin is dispersed as resin particles in the ink containing an aqueous medium. Whether it exists as resin particles can be confirmed, for example, by whether there is a peak corresponding to the resin particles when measuring the dispersed particle size (Z-average) of the ink with a particle size measuring device (e.g., Zataizer Nano S90 manufactured by Melvern).

[0078] The Tg of the water-dispersible resin is not particularly limited, but it is preferably low. This is to make it difficult for the flocked fiber substrate to become hard even after image formation and to more easily maintain the texture. Specifically, the Tg of the water-dispersible resin is preferably 50°C or lower, more preferably 0°C or lower, and even more preferably -35°C or lower. The lower limit value of the Tg of the water-dispersible resin is not particularly limited, but it can be, for example, -70°C or higher. The Tg of the water-dispersible resin can be measured by differential scanning calorimetry in accordance with JIS K 7121 at a heating rate of 10°C / min.

[0079] In addition, the water-dispersible resin preferably has an ionic group that pairs with the ionic group of the above-mentioned aggregating agent, and preferably has an anionic group. That is, the water-dispersible resin is preferably a water-dispersible resin having a water-dispersible anionic group. Examples of the anionic group include a carboxyl group, a sulfonic acid group, a phosphonic acid group, etc.

[0080] Examples of the water-dispersible resin having an anionic group may include (meth)acrylic resins, polystyrene resins, polyurethane resins, polyester resins, etc. having an anionic group. Among them, from the viewpoints of appropriately low Tg of the resin and flexibility, (meth)acrylic resins having an anionic group and polyurethane resins having an anionic group are preferable.

[0081] ((meth)acrylic resin having an anionic group) The (meth)acrylic resin having an anionic group is a polymer containing a structural unit derived from a (meth)acrylic monomer. The polymer may further contain a structural unit derived from another monomer copolymerizable with the (meth)acrylic monomer. And at least one of the (meth)acrylic monomer and the other monomer, preferably the (meth)acrylic monomer, has an anionic group. Note that the (meth)acrylic monomer is a monomer having a (meth)acryloyl group. (Meth)acrylic is a concept including both methacrylic and acrylic.

[0082] Examples of the (meth)acrylic monomer having an anionic group include acrylic acid and methacrylic acid. Examples of other (meth)acrylic monomers include (meth)acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and hydroxyethyl (meth)acrylate; (meth)acrylamides; (meth)acrylonitrile, etc.

[0083] Examples of other copolymerizable monomers include ethylenically unsaturated carboxylic acids (e.g., maleic acid, itaconic acid); styrenes (e.g., styrene, α-methylstyrene, vinyltoluene); vinyl saturated fatty acid esters (e.g., vinyl acetate, vinyl propionate); vinyl compounds (e.g., 1,4-divinyloxybutane, divinylbenzene, etc.); allyl compounds (e.g., diallyl phthalate, triallyl cyanurate, etc.) and other monofunctional monomers; polyfunctional (meth)acrylates such as diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, propylene glycol di(meth)acrylate, N,N'-methylenebis(acrylamide), etc., and difunctional or higher functional monomers such as polyfunctional acrylamides.

[0084] Among them, from the viewpoint of lowering the Tg of the (meth)acrylic resin, the (meth)acrylic monomer preferably contains acrylic acid and an alkyl acrylate. The alkyl acrylate is preferably a C4-12 alkyl acrylate, more preferably n-butyl acrylate and 2-ethylhexyl acrylate.

[0085] Examples of commercially available products of the (meth)acrylic resin include EMN-325 (Acryset manufactured by Nippon Shokubai Co., Ltd., acrylic elastomer, Tg: -50°C), EMN-326 (Acryset manufactured by Nippon Shokubai Co., Ltd., acrylic elastomer, Tg: -50°C), etc.

[0086] (Urethane resin having an anionic group) The urethane resin having an anionic group can exist as resin particles dispersed in an aqueous medium. The above urethane resin may be self-emulsified resin particles into which a hydrophilic group has been introduced, or forced emulsified resin particles that become water-dispersible by using an external emulsifier. From the viewpoint of suppressing bleed-out, the self-emulsified type is preferred.

[0087] The urethane resin having an anionic group may be any of a polyether-type urethane resin, a polyester-type urethane resin, and a polycarbonate-type urethane resin. Further, the urethane resin having an anionic group is preferably a self-emulsifying type. The self-emulsifying type urethane resin can be, for example, a polyaddition reaction product of a polyhydric alcohol having an anionic group and a polyvalent isocyanate.

[0088] Examples of commercially available products of the urethane resin having an anionic group include Takelac(R) W-6010 (polycarbonate-based / anionic type), Takelac(R) W-6020 (ether-based / anionic type), Takelac(R) W-6061 (ether-based / anionic type), Takelac(R) W-6110 (carbonate-based / anionic type), Takelac(R) W-405 (ester-based / anionic type), Takelac(R) W-605 (ester-based / anionic type), Takelac(R) WS-5000 (polyester-based / anionic type), Takelac(R) WS-4000 (polycarbonate-based / anionic type) (all manufactured by Mitsui Chemicals, Inc.), Superflex(R) 126 (ether / ester-based, anionic type), Superflex(R) 130 (ether-based, anionic type), Superflex(R) 150 (ether / ester-based, anionic type), Superflex(R) 300 (ether / ester-based, weak anionic type), Superflex(R) 420 (polycarbonate-based / anionic type), Superflex(R) 460 (polycarbonate-based / anionic type) (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and the like. The above anionic urethane resin may be of one kind or two or more kinds.

[0089] (General) The acid value of the water-dispersible resin is not particularly limited, but from the viewpoint of more easily suppressing stickiness, a lower value is preferable. Specifically, the acid value of the water-dispersible resin is preferably 8 mgKOH / g or more and 50 mgKOH / g or less, and more preferably 10 mgKOH / g or more and 30 mgKOH / g or less. The acid value of the water-dispersible resin can be measured according to JIS K 0070.

[0090] The average particle diameter of the water-dispersible resin used in the preparation of the ink can be, for example, 100 nm or less. The average particle diameter can be measured as, for example, the dispersed particle diameter (Z-average) in a Zataizer Nano S90 manufactured by Melvern.

[0091] The content of the water-dispersible resin is not particularly limited, but it is preferably 1% by mass or more and 20% by mass or less based on the ink. When the content of the water-dispersible resin is 1% by mass or more, it is easier to further enhance the fixing property of the ink to the raised fiber base material. When the content of the water-dispersible resin is 20% by mass or less, the texture is less likely to be impaired. From the same viewpoint, the content of the water-dispersible resin is more preferably 5% by mass or more and 15% by mass or less based on the ink.

[0092] The water content is, for example, 20% by mass or more and 70% by mass or less based on the ink, and preferably 30% by mass or more and 60% by mass or less.

[0093] 2-2-3. Other components The ink may further contain other components as necessary. Examples of other components include water-soluble organic solvents, pigment dispersants, surfactants, preservatives, fungicides, pH adjusters, and the like.

[0094] As the water-soluble organic solvent, the same ones as those used in the first treatment liquid can be used. The content of the water-soluble organic solvent is, for example, 20% by mass or more and 70% by mass or less based on the ink, and preferably 30% by mass or more and 60% by mass or less.

[0095] The pigment dispersant exists so as to surround the surface of the pigment particles in the ink or is adsorbed on the surface of the pigment particles to form a pigment dispersion liquid and disperse the pigment well. The pigment dispersant is preferably a polymer dispersant, and more preferably an anionic polymer dispersant.

[0096] An anionic polymer dispersant is a polymer dispersant having hydrophilic groups such as carboxyl groups, phosphorus-containing groups, and sulfonic acid groups, and preferably a polymer dispersant having a carboxyl group.

[0097] The polymer dispersant having a carboxyl group can be a polycarboxylic acid or its salt. Examples of polycarboxylic acids include (co)polymers of monomers selected from acrylic acid or its derivatives, maleic acid or its derivatives, itaconic acid or its derivatives, fumaric acid or its derivatives, and salts thereof. Examples of other monomers constituting the copolymer include styrene and vinyl naphthalene.

[0098] From the viewpoint of sufficiently dispersing pigment particles, the anionic group equivalent of the anionic polymer dispersant is preferably, for example, 1.1 meq / g or more and 3.8 meq / g or less. When the anionic group equivalent is within the above range, high pigment dispersibility can be easily obtained without increasing the molecular weight of the anionic polymer dispersant. The anionic group equivalent of the anionic polymer dispersant can be determined from the acid value. The acid value can be measured in accordance with JIS K0070.

[0099] The weight average molecular weight (Mw) of the polymer dispersant is not particularly limited, but is preferably 5000 or more and 30000 or less. When the Mw of the polymer dispersant is 5000 or more, it is easy to sufficiently disperse the pigment particles, and when it is 30000 or less, the ink does not thicken too much, so the permeability to the raised fiber substrate is hardly impaired. The Mw of the polymer dispersant can be measured by the same method as described above.

[0100] The content of the polymer dispersant may be in a range that can sufficiently disperse the pigment particles and has a viscosity that does not impair the permeability to the raised fiber substrate, and is not particularly limited, but is preferably 20% by mass or more and 100% by mass or less, more preferably 25% by mass or more and 60% by mass or less, based on the pigment.

[0101] As the surfactant, pH adjuster, and preservative, those similar to the surfactant, pH adjuster, and preservative that can be contained in the above-described first treatment liquid can be used respectively.

[0102] 2-2-4. Physical Properties The viscosity of the ink at 25°C is not particularly limited as long as the injectability by the inkjet method is good, but it is preferably 3 mPa·s or more and 20 mPa·s or less, and more preferably 4 mPa·s or more and 12 mPa·s or less. The viscosity of the ink can be measured at 25°C using an E-type viscometer.

[0103] 2-3. Second Treatment Liquid The second treatment liquid contains a silicone-based resin and water.

[0104] The silicone-based resin is preferably a water-dispersible silicone-based resin. This is for high water resistance and better suppression of stickiness. The water-dispersible silicone-based resin exists in a state of being dispersed as resin particles in an aqueous medium. Since the second treatment liquid is an aqueous medium containing water and an arbitrary water-soluble organic solvent, the above silicone-based resin is contained as resin particles.

[0105] The above silicone-based resin is a polymer containing a structural unit derived from polyorganosiloxane. The polymer may be a homopolymer composed of a structural unit derived from polyorganosiloxane, or a copolymer containing a structural unit derived from polyorganosiloxane and a structural unit derived from another polymerizable monomer (including macromonomer) copolymerizable therewith.

[0106] The above copolymer may be, for example, a graft copolymer in which structural units derived from polyorganosiloxane and (meth)acrylate esters or the like (polymerizable monomers) are graft-polymerized, or a copolymer in which the side chains or terminals of (meth)acrylic resins or the like are modified with polyorganosiloxane. Among them, a graft copolymer in which (meth)acrylate esters or the like are graft-polymerized onto a polymer containing structural units derived from polyorganosiloxane is preferred. Such a graft copolymer has a structure in which the polyorganosiloxane part forms the trunk and (meth)acrylate esters or the like form the branches, and is therefore more likely to be compatible with the water-dispersible resin contained in the ink, which is preferred. Note that the form of copolymerization is not limited to graft copolymerization, and may be random copolymerization or block copolymerization.

[0107] Further, the above silicone-based resin may have an ionic group. The ionic group possessed by the above silicone-based resin may be an ionic group that forms a pair with the ionic group possessed by the cutin fiber substrate (or the ionic group of the flocculant). For example, since the flocculant usually has a cationic group, the above silicone-based resin may be an anionic silicone-based resin having an anionic group. Examples of the anionic group are the same as those described above.

[0108] That is, it is preferable that the above silicone-based resin contains a structural unit derived from a polyorganosiloxane having a radical polymerizable group and a structural unit derived from another polymerizable monomer copolymerizable therewith.

[0109] Examples of the polyorganosiloxane having a radical polymerizable group include polyorganosiloxanes represented by the following formula (1).

Chemical formula

[0110] In the above formula (1), R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 10 carbon atoms. Y is a radically polymerizable group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group. X 1 and X 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or SiR 4 R 5 R 6 (R 4 、R 5 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R 6 represents a hydrocarbon group having 1 to 10 carbon atoms or a radically polymerizable group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group). m is an integer from 1 to 10,000. n is an integer of 1 or more. The siloxane chain may have a branch.

[0111] Examples of other polymerizable monomers include (meth)acrylic acid esters, vinyl acetate, urethane compounds having a radically polymerizable group, and the like. In this specification, (meth)acrylic represents acrylic, methacrylic, or both.

[0112] (Meth)acrylic acid esters are alkyl esters, hydroxyalkyl esters, or alkoxyalkyl esters of (meth)acrylic acid. Examples of (meth)acrylic acid esters include (meth)acrylic acid methyl, (meth)acrylic acid ethyl, (meth)acrylic acid isopropyl, (meth)acrylic acid n-propyl, (meth)acrylic acid n-butyl, (meth)acrylic acid isobutyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid isooctyl, (meth)acrylic acid n-octyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-methoxyethyl, and other (meth)acrylic acid esters. Among them, methyl methacrylate and 2-hydroxyethyl methacrylate are preferred.

[0113] Examples of the urethane compound having a radically polymerizable group include a compound obtained by reacting a polyol, a polyisocyanate, a silicone compound having two hydroxy groups, and an isocyanate compound having a (meth)acryloyl group.

[0114] Among these, as other polymerizable monomers, (meth)acrylate esters are preferably used.

[0115] In the above silicone-based resin, the content of the structural unit derived from polyorganosiloxane is preferably 50% by mass or more, more preferably 60% by mass or more and 95% by mass or less, based on the total amount of the structural units constituting the silicone-based resin. When the content of the structural unit derived from polyorganosiloxane is 50% by mass or more, the effect of reducing the friction coefficient derived from polysiloxane can be more easily obtained, and stickiness can be more suppressed. When the content of the structural unit derived from polyorganosiloxane is 95% by mass or less, for example, the adhesion with other compounds and the water-dispersible resin in the ink can be more easily enhanced due to the affinity.

[0116] The above silicone-based resin may further contain a structural unit derived from other polymerizable monomers other than the above. Examples of other polymerizable monomers other than the above include ethylenically unsaturated carboxylic acids such as (meth)acrylic acid and styrenes. For example, from the viewpoint of exhibiting anionic properties, the silicone-based resin may further contain a structural unit derived from an ethylenically unsaturated carboxylic acid such as (meth)acrylic acid.

[0117] Graft copolymerization can be carried out by a known method. For example, polyorganosiloxane represented by the above formula (1) and a copolymerizable compound such as (meth)acrylate ester are emulsified and dispersed in water, and polymerized in the presence of a radical polymerization initiator to carry out graft copolymerization.

[0118] Examples of commercially available silicone-(meth)acrylic copolymers include Charine E-370, LC190, R-170, R170S, FE-230N, FE-502, R-170BX (manufactured by Nisshin Chemical Industry Co., Ltd.), and the like. Examples of commercially available silicone-urethane copolymers include Charine RU-911 (manufactured by Nisshin Chemical Industry Co., Ltd.). Examples of commercially available silicone-vinyl acetate copolymers include Charine 1827 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0119] The glass transition temperature (Tg) of the above silicone-based resin is not particularly limited, but is preferably, for example, 0°C or higher and 150°C or lower. When the Tg of the silicone-based resin is 0°C or higher, stickiness can be further suppressed. When the Tg of the silicone-based resin is 150°C or lower, it is easier to enhance the adhesion to the ink pool and less likely to impair the texture. Stickiness can be further suppressed. From the same viewpoint, the Tg of the silicone-based resin is more preferably 30°C or higher and 120°C or lower. The Tg of the above silicone-based resin can be measured in the same manner as the Tg of the above water-dispersible resin.

[0120] The Tg of the above silicone-based resin can be adjusted by the type and amount of modification, for example, the content of structural units derived from other compounds such as (meth)acrylate esters. When the content of structural units derived from the other compound is large, the Tg tends to be low.

[0121] The average particle diameter of the above silicone-based resin used in the preparation of the second treatment liquid is not particularly limited, but is preferably, for example, 150 nm or more and 300 nm or less. The average particle diameter is the average value of the primary particle diameters. The average particle diameter can be measured in the same manner as described above.

[0122] The acid value of the silicone-based resin is not particularly limited, but from the viewpoint of further enhancing water resistance, it is preferably low. Specifically, the acid value of the silicone-based resin is preferably lower than the acid value of the water-dispersible resin contained in the ink, more preferably 100 mgKOH / g or less, and even more preferably 0.1 mgKOH / g or more and 50 mgKOH / g or less. The acid value of the silicone-based resin can be measured according to JIS K 0070.

[0123] The content of the silicone-based resin in the second treatment liquid is as described above.

[0124] The second treatment liquid preferably further contains a water-soluble organic solvent. As the water-soluble organic solvent, the same solvents as those contained in the first treatment liquid and the ink can be used.

[0125] The content of the water-soluble organic solvent is preferably, for example, 10% by mass or more and 65% by mass or less, more preferably 20% by mass or more and 45% by mass or less, based on the second treatment liquid.

[0126] The content of water is 30% by mass or more and 85% by mass or less, preferably 50% by mass or more and 75% by mass or less, based on the second treatment liquid.

[0127] The second treatment liquid may further contain surfactants, pH adjusters, preservatives, etc. similar to those of the first treatment liquid and the ink described above.

[0128] Also, from the viewpoint of making it easier for the silicone-based resin to be unevenly distributed on the surface of the image forming object, the second treatment liquid preferably does not substantially contain color materials such as pigments.

Examples

[0129] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[0130] 1. Materials 1-1. Resin having a cationic group · Cationic resin A-1: PAS-M-1L manufactured by Nittobo Medical Co., Ltd., a polymer of methyldiallylamine hydrochloride · Cationic resin A-2: MPT-60 manufactured by Mitsubishi Pencil Co., Ltd., a quaternary salt of an alkylamine·epichlorohydrin adduct

[0131] 1-2. Water-dispersible resin having an anionic group · Anionic resin B-1: EMN-325E manufactured by Nippon Shokubai Co., Ltd. (acrylic resin, acid value 14 mgKOH / g, Tg = -50 °C) · Anionic resin B-2: EF-021 manufactured by Nippon Shokubai Co., Ltd. (acrylic resin, acid value 15 mgKOH / g, Tg = -2 °C) · Anionic resin B-3: Superflex 150 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (urethane resin, acid value 15 mgKOH / g, Tg = 40 °C) · Anionic resin B-4: Superflex 470 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (urethane resin, acid value 10 mgKOH / g, Tg = -31 °C)

[0132] 1-3. Modifying agent · C-1: Charine E-370 manufactured by Nisshin Chemical Industry Co., Ltd. (silicone·acrylic graft copolymer, anionic, Tg = 105 °C) · C-2: Charine FE-502 manufactured by Nisshin Chemical Industry Co., Ltd. (silicone·acrylic graft copolymer, anionic, Tg = -16 °C) · C-3: EF-005 manufactured by Nippon Shokubai Co., Ltd. (anionic, acrylic resin) · C-4: K-2020 manufactured by Nippon Shokubai Co., Ltd. (oxazoline group-containing emulsion, crosslinking agent) · C-5: F-559 manufactured by DIC Corporation (fluorine group·hydrophilic group·lipophilic group-containing oligomer, fluorine-based surface modifier) · C-6: F-569 manufactured by DIC Corporation (fluorine group·hydrophilic group-containing oligomer, fluorine-based surface modifier)

[0133] (Tg) The Tg of each resin is the value measured at a heating rate of 10 °C / min in accordance with JIS K 7121 by differential scanning calorimetry.

[0134] (Acid value) The acid value of each resin is a value measured in accordance with JIS K 0070.

[0135] 1-4. Water-soluble organic solvents · Ethylene glycol · Propylene glycol · Glycerin

[0136] 1-5. Other components · Olfin E1010 (manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol-based surfactant) · Proxel GXL (manufactured by Lonza Japan, 1,2-benzisothiazolin-3-one, mildew preventive)

[0137] 2. Preparation of each liquid 2-1. Preparation of treatment liquid 1 As shown in Table 1, each component was mixed to a total of 100 parts by mass, and treatment liquids 1-1 and 1-2 were prepared. The compositions of treatment liquids 1-1 and 1-2 are shown in Table 1.

[0138]

Table 1

[0139] 2-2. Preparation of ink (Preparation of pigment dispersion) As a pigment dispersant, 13.5 parts by mass of Cab-0-Jet 4637 (manufactured by CABOT) was added to 20 parts by mass of ethylene glycol and 48.5 parts by mass of ion-exchanged water. To this solution, 18.0 parts by mass of Pigment Black 7 was added as a black pigment and premixed. Then, it was dispersed using a sand grinder filled with 0.5 mm zirconia beads at a volume ratio of 50% to prepare a black pigment dispersion with a pigment solid content of 18.0% by mass.

[0140] (Preparation of ink) As shown in Table 2, each component was mixed to a total of 100 parts by mass, and inks 1 to 4 were prepared. For the pigment dispersion, the total mass part of the solid content of the pigment dispersion is shown.

[0141] The compositions of Inks 1 to 4 are shown in Table 2.

[0142]

Table 2

[0143] 2-3. Preparation of Treatment Liquid 2 As shown in Table 3, each component was mixed to a total of 100 parts by mass, and Treatment Liquids 2-1 to 2-7 were prepared. The compositions of Treatment Liquids 2-1 to 2-7 are shown in Table 3.

[0144]

Table 3

[0145] 3. Image Formation and Evaluation <Examples 1 to 6, Comparative Examples 1 to 8> 3-1. Image Formation (First Step) As an image forming apparatus, a simple printing test equipped with an inkjet head KM1024i (manufactured by Konica Minolta) was prepared. The treatment liquid 1 and ink shown in Table 4 were set in this simple tester.

[0146] First, as a pile fiber substrate, polyester calico (pile length 800 μm, pile density 250 pieces / cm 2 , thickness 100 μm) was prepared. On the pile surface of this pile fiber substrate, the treatment liquid 1 and ink shown in Table 4 were continuously applied in this order by an inkjet method. The discharge of the treatment liquid 1 and ink from the inkjet head was performed at a main scanning of 540 dpi × a sub-scanning of 720 dpi, respectively. Note that dpi represents the number of ink droplets (dots) per 2.54 cm. The discharge frequency was set to 22.4 kHz.

[0147] (Second Step) Next, the pile fiber substrate to which the treatment liquid 1 and ink were applied was dried at 150 °C for 3 minutes in a belt conveyor dryer to obtain a 100% solid image of 200 mm × 200 mm. Incidentally, the adhesion amounts of the treatment liquid 1 and the ink (the adhesion amount in the wet state including the solvent) were 15 g / m 2 and 30 g / m 2 respectively. These adhesion amounts were determined from the ink ejection amounts.

[0148] (Third step) On the other hand, a bath filled with the treatment liquid 2 shown in Table 4 was prepared. The solid image formation was immersed in this treatment liquid 2 at room temperature (23°C) for 30 seconds and then mangle-treated. The amount of the added modification component (dry state) was 2 g / m 2 . Incidentally, the adhesion amount (dry state) of the modification component of the treatment liquid 2 of Comparative Example 1 ejected by inkjet was 0.6 g / m 2 .

[0149] Then, it was dried at 150°C for 3 minutes with a belt conveyor dryer to obtain a 100% solid image formation of 200 mm × 200 mm.

[0150] 3-2. Evaluation The texture, stickiness, and bleeding of the obtained image formation were evaluated by the following methods.

[0151] (1) Texture The sensory evaluation of the texture of the obtained image formation was performed by 5 people. Based on the number of people who felt that the raised fiber substrate after image formation was harder than the raised fiber substrate before image formation, the texture was evaluated according to the following criteria. A: The number of people who felt that it became harder after image formation was 0 to 1 person. B: The number of people who felt that it became harder after image formation was 2 to 3 people. C: The number of people who felt that it became harder after image formation was 4 people. D: The number of people who felt that it became harder after image formation was 5 people.

[0152] (2) Stickiness The obtained image formation was folded in half so that the image formation surface (fuzzy surface) faced inward, a 1-kg weight was placed on it from above, and it was held for 5 minutes. Then, the weight was removed. The part where the weight had been placed was pinched, and it was observed whether the image surfaces were stuck together due to stickiness, and evaluated according to the following criteria. A: The image formation surfaces did not stick together and were easily peeled off. B: The image formation surfaces slightly stuck together but peeled off after 30 seconds. C: The image formation surfaces stuck together and did not peel off even after 30 seconds had passed. A and B are within the acceptable range.

[0153] (3) Bleeding The boundary between the printed part and the non-printed part of the obtained image formation was visually confirmed and evaluated according to the following criteria. A: No bleeding was observed. B: Slight bleeding was observed. C: The bleeding was significant and no image could be formed.

[0154] The image formation conditions and evaluation results of Examples 1 to 6 and Comparative Examples 1 to 8 are shown in Table 4.

[0155]

Table 4

[0156] As shown in Table 4, it can be seen that the image formations of Examples 1 to 6, to which Treatment Liquid 1 was applied by inkjet and Treatment Liquid 2 was applied by dipping treatment, can significantly suppress stickiness without degrading the texture. It can also be seen that no bleeding occurs.

[0157] On the other hand, it can be seen that stickiness cannot be suppressed when the third step using Treatment Liquid 2 is not performed or when Treatment Liquid 2 is applied by inkjet (Comparative Examples 1 and 2). Also, when Treatment Liquid 2 is applied by dipping treatment, it can be seen that the texture is poor (Comparative Example 3).

[0158] In Comparative Examples 5 to 8 where a treatment liquid containing a modifying component that is not a silicone-based resin is used as the treatment liquid 2, it can be seen that stickiness cannot be suppressed. Specifically, in C-3 to C-6, it is presumed that stickiness could not be suppressed in any of them because the components for suppressing stickiness contained in the treatment liquid 2 did not sufficiently remain on the surface. In particular, when a crosslinking agent C-4 or a fluorine-containing surface modifier C-5 is used, it can be seen that the texture deteriorates because the connection between the resins becomes too strong.

Industrial Applicability

[0159] According to the present invention, it is possible to provide an image forming method that can use existing equipment, suppress a decrease in texture and bleeding, and suppress the stickiness of a raised fiber substrate.

Claims

1. A first step of applying, by an inkjet method, an ink containing a pigment, a water-dispersible resin, and water, and a first treatment liquid containing a flocculant for aggregating the pigment or the water-dispersible resin and water onto a cutin fiber base material having cutin; A second step of drying the cutin fiber base material to which the first treatment liquid and the ink have been applied; A third step of immersing the dried cutin fiber base material in a second treatment liquid containing a silicone-based resin and water comprising An image forming method.

2. The flocculant contains a resin having a cationic group, The image forming method according to claim 1.

3. The water-dispersible resin contains a water-dispersible resin having an anionic group, The image forming method according to claim 2.

4. The glass transition temperature of the water-dispersible resin is 0 ° C or lower, The image forming method according to claim 3.

5. The water-dispersible resin contains a urethane resin, The image forming method according to claim 3.

6. The silicone-based resin is a water-dispersible silicone-based resin, The image forming method according to claim 1.

7. The water-dispersible silicone-based resin contains a copolymer containing a structural unit derived from a polyorganosiloxane having a radically polymerizable group and a structural unit derived from a (meth)acrylate ester, The image forming method according to claim 6.

8. The glass transition temperature of the water-dispersible silicone-based resin is 30 ° C or higher and 120 ° C or lower, The image forming method according to claim 6.

9. The first treatment liquid and the ink each further contain a glycol-based solvent having a boiling point of 180° C. or higher. The image forming method according to claim 1.

10. The image forming method according to claim 1, wherein the length of the raised hair of the raised hair fiber substrate is 200 μm or more and 1000 μm or less.

Images