Recording method

Abstract

Provided is a recording method that is excellent in color development and rubbing fastness. A recording method according to an embodiment of the present invention records on a cloth, and has: an ink adhering step of adhering droplets of an ink composition containing a pigment and a resin particle to the cloth; and a treatment liquid adhering step of adhering droplets of a treatment liquid containing a crosslinking agent to the cloth, the maximum weight of each of the droplets of the ink composition being 30 ng or less, the maximum weight of each of the droplets of the treatment liquid being 30 ng or less, and the weight of the droplets of the treatment liquid being equal to or less than the weight of the droplets of the ink composition.

Description

Technical Field

[0001] This invention relates to a recording method. Background Technology

[0002] In the prior art, when printing fabrics by dyeing substrates such as fabrics with pigments or other colorants using inkjet printing, a technique is known to pretreat the substrate using a treatment liquid containing cationic compounds or the like to improve the color development of the pigments. A method for recording the pretreatment and ink adhesion processes using a recording device has been studied.

[0003] For example, Patent Document 1 describes a wet-on-wet inkjet printing method in which, in printing using an ink composition containing pigments, the process from attaching a pretreatment liquid containing a polyvalent metal compound to attaching ink is carried out without a drying process.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent document 1: Japanese Patent Application Publication No. 2016-089288.

[0007] However, this method suffers from the problem that color development and rubbing fastness are easily degraded. Summary of the Invention

[0008] One aspect of the recording method involved in this invention is a recording method relative to cloth, comprising:

[0009] The ink adhesion process involves adhering droplets of an ink composition containing pigments and resin particles to the fabric; and

[0010] The treatment liquid adhesion process involves attaching droplets of a treatment liquid containing a crosslinking agent to the fabric.

[0011] The maximum weight of each droplet of the ink composition is less than 30 ng.

[0012] The maximum weight of each droplet of the treatment solution is less than 30 ng.

[0013] The droplet weight of the processing liquid is less than or equal to the droplet weight of the ink composition. Attached Figure Description

[0014] Figure 1 This is a schematic perspective view of an inkjet printing apparatus applicable to the recording method described in this embodiment.

[0015] Figure 2 This is a schematic diagram showing an example of the configuration of the inkjet printhead in an inkjet printing apparatus.

[0016] Figure 3 This is a schematic diagram showing an example of the configuration of the inkjet printhead in an inkjet printing apparatus.

[0017] Figure 4 This is a schematic diagram showing an example of the configuration of the inkjet printhead in an inkjet printing apparatus.

[0018] Symbol Explanation

[0019] 1. Printer; 2. Fabric; 3 (3a, 3b) Inkjet head; 4. Carriage; 5. Main scanning mechanism; 6. Pressure roller; 7a, 7b, 7c, 7d, 7e, 7f, Liquid cartridge; 8. Synchronous belt; 9. Motor; 10. Guide shaft. Detailed Implementation

[0020] The following describes embodiments of the present invention. These embodiments are used to illustrate examples of the present invention. The present invention is not limited to any of the following embodiments, and includes various modifications implemented without changing the spirit of the invention. Furthermore, all configurations described below are not necessarily essential to the present invention.

[0021] 1. Recording Method

[0022] One embodiment of the present invention relates to a recording method relative to a fabric, comprising: an ink adhesion step, wherein droplets of an ink composition containing pigment and resin particles are adhered to the fabric; and a treatment liquid adhesion step, wherein droplets of a treatment liquid containing a crosslinking agent are adhered to the fabric, wherein the maximum weight of each droplet of the ink composition is 30 ng or less, the maximum weight of each droplet of the treatment liquid is 30 ng or less, and the weight of the treatment liquid droplets is less than or equal to the weight of the ink composition droplets.

[0023] In existing technologies, when printing fabrics using inkjet printing to dye substrates such as fabrics with pigments or other colorants, a known technique involves pretreating the substrate with a treatment solution containing cationic compounds to improve the color development of the pigments. Furthermore, pretreatment in inkjet pigment printing typically utilizes a separate device / equipment and employs methods such as immersion. However, this method not only requires a separate device / equipment, but also makes the process cumbersome and complex, necessitating proprietary technology. Additionally, the discharge of waste liquid is undesirable from an environmental impact perspective.

[0024] Therefore, in inkjet printing, a recording method (pretreatment process flow) for a pretreatment liquid step to reduce ink bleeding and improve color development, and an ink adhesion step, using a single recording device, was studied. This method simplifies the process and eliminates waste liquid discharge. In particular, the wet-on-wet method, which omits the drying process between the pretreatment liquid step and the ink adhesion step, has advantages in terms of device miniaturization and high speed. However, it also suffers from problems such as bleeding, deterioration of color development, and rubbing fastness. This is presumably due to increased moisture content on the recording medium. Specifically, it is speculated that high moisture content on the recording medium leads to bleeding, hinders the coagulation reaction between the treatment liquid and the ink, thus deteriorating color development, and results in insufficient drying, leading to deterioration of rubbing fastness.

[0025] In contrast, the inventors have recently discovered that by including a crosslinking agent in the treatment liquid and applying the ink and treatment liquid in a specific manner, excellent color development and rubbing fastness can be achieved. Specifically, according to the recording method of this embodiment, by including a crosslinking agent in the treatment liquid and applying the ink and treatment liquid at a rate of 30 ng / drop or less, with the droplet size of the treatment liquid being less than the droplet size of the ink, good color development and rubbing fastness can be achieved. By making the droplet size as small as 30 ng or less, and by making the droplet size of the treatment liquid less than the droplet size of the ink, the ink and treatment liquid are easily mixed. This facilitates the reaction between the resin particles in the ink and the crosslinking agent in the treatment liquid, effectively causing the ink to thicken and coagulate, resulting in good color development as the ink remains near the surface of the fabric. Furthermore, the crosslinking of the crosslinking agent toughens the ink layer, thereby improving rubbing fastness.

[0026] The recording method described in this embodiment is performed relative to fabric. There are no particular limitations on the raw materials used to constitute the fabric; examples include natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; biodegradable fibers such as polylactic acid; and blends of these fibers.

[0027] The preferred fabric has hydroxyl groups. Examples of such fabrics include cellulose-containing fabrics such as cotton and linen, and fabrics containing polyurethane. When the fabric has hydroxyl groups, a crosslinking reaction can occur between the crosslinking agent contained in the treatment liquid described later and the hydroxyl groups of the fabric. This can sometimes result in improved color development due to thickening and coagulation, and improved rubbing adhesion due to improved adhesion between the fabric and the ink layer.

[0028] The fabric can be any fabric made from the aforementioned fibers, such as woven fabric, knitted fabric, or nonwoven fabric. Furthermore, the weight per unit area of ​​the fabric used in this embodiment is not particularly limited; it can be 1.0 oz or more and 10.0 oz or less, preferably 2.0 oz or more and 9.0 oz or less, more preferably 3.0 oz or more and 8.0 oz or less, and even more preferably 4.0 oz or more and 7.0 oz or less. If the weight per unit area of ​​the fabric is within this range, good recording is possible. Moreover, the recording method described in this embodiment is applicable to various fabrics with different weights per unit area and allows for good printing.

[0029] In this embodiment, the types of fabrics include cloth, clothing, and other accessories. Clothing includes textiles, woven fabrics, and non-woven fabrics. Clothing and other accessories include sewn T-shirts, handkerchiefs, scarves, towels, tote bags, cloth bags, curtains, sheets, bedspreads, wallpaper, and other furniture, as well as fabric before and after cutting, which are used as components before sewing. Examples of these methods include rolling them into long strips, cutting them into specified sizes, and shaping them into specific product shapes.

[0030] As fabric, cotton fabric pre-dyed with dyes can also be used. Examples of dyes for pre-dyed fabrics include water-soluble dyes such as acid dyes and basic dyes, disperse dyes used in combination with dispersants, and reactive dyes. When using cotton fabric as a pre-dyed fabric, reactive dyes suitable for dyeing cotton are preferred.

[0031] The following describes each step of the recording method according to this embodiment.

[0032] 1.1 Ink Adhesion Process

[0033] The recording method described in this embodiment includes an ink adhesion step of adhering droplets of an ink composition containing pigments and resin particles to the aforementioned fabric.

[0034] 1.1.1 Droplet weight of the ink composition

[0035] In the recording method described in this embodiment, the maximum weight of each droplet of the ink composition is 30 ng or less, and the weight of the droplets of the processing liquid described later is less than or equal to the weight of the droplets of the ink composition.

[0036] The maximum weight of each droplet of the ink composition is preferably 29 ng or less, more preferably 28 ng or less, further preferably 27 ng or less, even more preferably 26 ng or less, particularly preferably 25 ng or less, and even more preferably 24 ng or less. The lower limit of the maximum weight of each droplet of the ink composition is not particularly limited, but it is preferably 11 ng or more, more preferably 15 ng or more, further preferably 19 ng or more, and particularly preferably 23 ng or more. When the maximum weight of each droplet of the ink composition is within the above range, it sometimes makes the ink and the treatment liquid easier to mix, further improving color development and rubbing fastness.

[0037] Furthermore, if the resolution and occupancy of the image are known, the weight of each droplet of the ink composition and the processing liquid (described later) can be determined based on the change in liquid volume. For example, it can be calculated as follows: ink ejection rate [ng / drop] = ink adhesion amount per unit area [mg / inch]. 2 ] / (resolution[drop / inch] 2 × Market Share × 10 -6 In addition, "occupancy rate" refers to the value calculated according to the formula: Occupancy Rate (%) = Actual Number of Recorded Points / (Vertical Resolution × Horizontal Resolution) × 100 (where "Actual Number of Recorded Points" is the actual number of recorded points per unit area, and "Vertical Resolution" and "Horizontal Resolution" are the resolutions per unit area, respectively).

[0038] In the recording method described in this embodiment, the droplet weight of the treatment liquid is less than or equal to the droplet weight of the ink composition, and preferably the droplet weight of the treatment liquid is smaller than the droplet weight of the ink composition. In this manner, the ink and treatment liquid are easier to mix, and the crosslinking agent contained in the treatment liquid can be more evenly coated on the fabric, thus resulting in better color development and rubbing fastness.

[0039] Furthermore, the comparison between the droplet weight of the ink composition and the droplet weight of the treatment liquid is a comparison between the average weight of the droplets of the ink composition attached per unit area and the average weight of the droplets of the treatment liquid attached per unit area.

[0040] Furthermore, the amount of ink composition adhering to the fabric is preferably 10–21 mg / inch per unit area of ​​the recording area. 2 More preferably 12–20 mg / inch 2 More preferably 14–19 mg / inch 2 Especially preferred is 15–18 mg / inch 2 .

[0041] 1.1.2 Process Interval

[0042] In the recording method of this embodiment, it is preferable that the time difference between the ink application step and the processing liquid application step (described later) is within 5 seconds. When the ink application step and the processing liquid application step are performed with such a time difference, a wet-on-wet method can be used, where the second droplet is applied before the first droplet dries. Furthermore, the second droplet is the processing liquid when the first droplet is an ink composition, and vice versa. While the wet-on-wet method has advantages in terms of device miniaturization and high speed, it also suffers from problems such as bleeding, deterioration of color development, and rubbing fastness. However, according to the recording method of this embodiment, even with this wet-on-wet method, color development and rubbing fastness are excellent, and bleeding is suppressed. In addition, in the recording method of this embodiment, if the time difference between the above-mentioned steps is within 5 seconds, the reaction between the ink and the processing liquid is easier to occur, tending to result in better color development and rubbing fastness.

[0043] In this invention, the time difference between the ink application process and the treatment liquid application process refers to the time difference from the last spraying of the treatment liquid to the initial spraying of the ink composition. Specifically, it refers to the time difference for the same area of ​​the fabric from the last spraying of the treatment liquid to the initial spraying of the ink composition.

[0044] Furthermore, in the following description, "alternating spraying" refers to the action of adhering the ink composition and processing liquid to the same scanned area of ​​the fabric through the same main scan (a scan in which the inkjet head moves in a direction perpendicular to the fabric transport direction), thereby forming a layer containing the ink composition and processing liquid. "Pre-spraying" refers to the action of adhering the ink composition and processing liquid to the same scanned area of ​​the fabric through different main scans, thereby stacking a layer containing the processing liquid and a layer containing the ink composition. In particular, when a layer containing the processing liquid is formed first, and then a layer containing the ink composition is stacked, it is called "processing liquid pre-spraying".

[0045] In the case of alternating spraying, the time difference between the ink application step and the treatment liquid application step is preferably 1 second or less, more preferably 0.8 seconds or less, even more preferably 0.6 seconds or less, and particularly preferably 0.4 seconds or less. The lower limit is not particularly limited, but it is preferably 0.01 seconds or more, more preferably 0.1 seconds or more. In the case of alternating spraying, the time difference between the ink application step and the treatment liquid application step is particularly preferably 0.3 seconds. With such a time difference, the reaction between the ink and the treatment liquid is easier to occur, tending to result in better color development and rubbing fastness.

[0046] When the treatment liquid is sprayed first, the time difference between the ink adhesion step and the treatment liquid adhesion step is preferably 4.9 seconds or less, more preferably 4.8 seconds or less, even more preferably 4.7 seconds or less, and particularly preferably 4.6 seconds or less. The lower limit is not particularly limited, but it is preferably 3.0 seconds or more, more preferably 3.5 seconds or more, even more preferably 4.0 seconds or more, particularly preferably 4.2 seconds or more, and even more preferably 4.4 seconds or more. When the treatment liquid is sprayed first, the time difference between the ink adhesion step and the treatment liquid adhesion step is particularly preferably 4.5 seconds. With such a time difference, the reaction between the ink and the treatment liquid is easier to occur, tending to result in better color development and rubbing fastness.

[0047] 1.1.3 Adhesion Method

[0048] 1.1.3.1 Alternating spray

[0049] In the recording method of this embodiment, the processing liquid adhesion process and the ink adhesion process described later are performed using an inkjet method. In the inkjet method, multiple main scans are performed to record by moving the inkjet head in a direction perpendicular to the fabric transport direction. Preferably, the processing liquid and ink composition are adhered to the same scanning area of ​​the fabric by the same main scan, and the same main scan is performed multiple times on the same scanning area.

[0050] This method allows for alternating spraying. That is, a layer containing the ink composition and treatment liquid is applied to a specific area of ​​the fabric using a single main scan, followed by another main scan where an overlapping layer of the ink composition and treatment liquid is applied on top. Because the treatment liquid and ink composition are alternately layered (in a layered fashion), the components mix more easily, facilitating the reaction and resulting in superior color development, rubbing fastness, and bleed suppression.

[0051] In addition, inkjet printing refers to a recording method in which droplets of ink or the like are ejected from the nozzle of an inkjet head of an inkjet recording device and applied to a recording medium.

[0052] When the same master scan is performed multiple times on the same scanning area, the master scan used to adhere the ink composition and processing liquid passes over the same area of ​​the fabric multiple times. The more scans, the more times (multiple passes) the ink and processing liquid can be adhered to the desired area, and there is a tendency for the image quality of the resulting record to be further improved.

[0053] Furthermore, when recording over any area, the number of times the inkjet head passes over that area is called a "stroke." For example, in the case of performing four main scans over the same area to allow the ink composition and processing liquid to adhere, the number of strokes is called four strokes, etc. For example, in Figure 3 In this method, when the length of a single sub-scan in the sub-scanning direction SS (T1, T2) is one-quarter of the length of the nozzle array in the sub-scanning direction SS, four scans are performed on a rectangular scanning area that is one sub-scan length in the sub-scanning direction SS and extends along the main scanning direction MS (S1, S2). The number of scans during this observation is referred to as the scan number or the number of passes, etc. The number of scans is 2 or more, preferably 3 or more, more preferably 4 or more. In addition, the number of scans is preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and especially preferably 4 or less. According to the recording method according to this embodiment, even if the number of scans is within the above range, there is a tendency for better color development, rubbing fastness, and suppression of bleeding.

[0054] Furthermore, in the aforementioned alternating spraying, a layer containing the treatment liquid can be formed using a main scan different from the main scan used to form the layer containing the ink composition and the treatment liquid, thereby stacking the layers containing the ink composition and the treatment liquid together. In this way, by forming the layer containing the treatment liquid, color development and rubbing fastness are sometimes further improved. The formation of the layer containing the treatment liquid can be performed before or after the formation of the layer containing the ink composition and the treatment liquid, but it is preferred to perform it beforehand.

[0055] 1.1.3.2 Spray first

[0056] In the recording method described in this embodiment, the processing liquid adhesion process and the ink adhesion process described later are performed using an inkjet method. The inkjet method is a method of recording by moving the inkjet head multiple times in a direction perpendicular to the fabric transport direction. Alternatively, the processing liquid and ink composition can be adhered to the same scanning area of ​​the fabric through different main scans.

[0057] In this method, pre-spraying can be performed, thereby enabling the layer containing the treatment liquid and the layer containing the ink composition to be formed in layers. In the recording method according to this embodiment, even with such pre-spraying, good color development, rubbing fastness, and bleed suppression are achieved.

[0058] Furthermore, in the first spraying, the order of the ink composition and the treatment liquid is not limited as long as they are attached by different main scans, but it is more preferable to spray the treatment liquid on which the ink composition is attached first.

[0059] In pre-jet printing, multiple different master scans can be performed on the same scanning area to adhere the ink composition and processing liquid to the scanning area. For example, it is possible to record the processing liquid in four strokes, and then record the ink composition in four strokes. Furthermore, the number of strokes in pre-jet printing can also be set independently for the ink composition and processing liquid.

[0060] 1.1.3.3 Other attachment methods

[0061] The above-mentioned alternating spraying and first spraying uses a serial inkjet head, but a row inkjet head can also be used for ink adhesion and treatment liquid adhesion processes.

[0062] That is, in the recording method of this embodiment, the processing liquid adhesion process and the ink adhesion process described later are performed by inkjet printing. The inkjet printing method may also use an inkjet head (line head) with a length of more than the recording width of the fabric to scan the conveyed fabric once.

[0063] In this line recording method, the ink composition and processing liquid can be sprayed and adhered to the fabric while the positions of the line head and the fabric are moved relative to each other in a scanning direction (the longitudinal direction of the fabric, the transport direction of the fabric) that intersects with the width direction of the fabric.

[0064] 1.1.4 Ink Composition

[0065] The ink composition used in the recording method according to this embodiment contains pigments and resin particles. Hereinafter, the components contained in the ink composition used in the recording method according to this embodiment will be described. Furthermore, it should be noted that the preparation of each component of the ink composition can be carried out independently of the processing liquid described later.

[0066] 1.1.4.1 Pigments

[0067] The ink composition used in the recording method according to this embodiment contains pigment. For example, inorganic pigments or organic pigments can be used as pigments. Furthermore, pigment refers to a type of colorant. Examples of colorants include pigments and dyes.

[0068] As inorganic pigments, there are no particular restrictions, but examples include carbon black such as furnace black, lamp black, acetylene black, and channel black; and white inorganic oxides such as iron oxide, titanium oxide, zinc oxide, and silicon dioxide.

[0069] Examples of carbon blacks include CI (Colour Index Generic Name) Pigment Black 1, 7, and 11. Commercially available carbon blacks are also available, such as Mitsubishi Chemical's No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B; Columbia Carbon's Raven (registered trademark) 5750, 5250, 5000, 3500, 1255, and 700; and CABOT's Rega1 (registered trademark) 40. 0R, 330R, 660R, Mogul (registered trademark) L, Monarch (registered trademark) 700, 800, 880, 900, 1000, 1100, 1300, 1400, etc., Degussa pigments FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex (registered trademark) 35, U, V, 140U, Extra Black 6, 5, 4A, 4, etc.

[0070] Examples of organic pigments include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthraquinone pigments, anthrone pigments, tanstanone pigments, yellow anthrone pigments, perylene pigments, pyrrolopyrrole dione pigments, violet ketone pigments, quinacridone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethyl base pigments, or azo pigments.

[0071] The following pigments can be listed as specific examples of organic pigments.

[0072] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 15:34, 16, 22, 60, etc.; CI Vat Blue 4, 60, etc., and preferably one or more mixtures selected from the group consisting of CI Pigment Blue 15:3, 15:4 and 60.

[0073] Examples of magenta pigments include CI pigment red 5, 7, 12, 48(Ca), 48(Mn), 57(Ca), 57:1, 112, 122, 123, 168, 184, 202, CI pigment violet 19, etc., and preferably one or more mixtures selected from the group consisting of CI pigment red 122, 202 and 209, CI pigment violet 19.

[0074] Examples of yellow pigments include CI pigment yellows 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151, 154, 155, 180, and 185. A preferred example is a mixture of one or more of CI pigment yellows 74, 109, 110, 128, 138, 150, and 180.

[0075] Other colors of pigment can also be used. For example, orange pigment, green pigment, etc.

[0076] Pigments can be used alone or in combination of two or more.

[0077] Furthermore, for pigments, in order to improve their dispersibility in ink compositions, it is preferable to perform surface treatment on the pigments or to incorporate dispersants, etc.

[0078] Surface treatment of pigments refers to the process of directly or indirectly bonding carbonyl, carboxyl, aldehyde, hydroxyl, sulfonyl, ammonium, and other functional groups formed by their salts to the surface of the pigment through physical or chemical treatment.

[0079] When a dispersant is incorporated into an ink composition, it is preferable to use a dispersant having both a hydrophobic portion (hydrophobic group) and a hydrophilic portion (hydrophilic group) in its molecular structure. This type of dispersant has the effect of the hydrophobic portion adsorbing onto the surface of pigment particles, while the hydrophilic portion is oriented towards the aqueous medium side of the ink composition. Through this effect, there is a tendency for the pigment to be contained more stably as a dispersion in the ink composition.

[0080] There are no particular limitations on such dispersants. Examples include acrylic resins, styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid resins, and their salts, aromatic sulfonates, and formaldehyde condensates. One or more products selected from the group consisting of these can be used. Alternatively, commercially available products can also be used as dispersants.

[0081] Alternatively, methods can be used to impart dispersibility to pigment particles by covering them with resins or similar materials. Methods for covering pigment particles include acid precipitation, phase inversion emulsification, and microemulsion polymerization.

[0082] The pigment content can be adjusted appropriately according to the application, but relative to the total amount of the ink composition, it is preferably 0.1% by mass or more and 17.0% by mass or less, more preferably 0.2% by mass or more and 15.0% by mass or less, even more preferably 1.0% by mass or more and 10.0% by mass or less, and particularly preferably 2.0% by mass or more and 5.0% by mass or less. If the pigment content is within the above range, there is a tendency to further improve the ejection performance when using inkjet printing.

[0083] In addition, the ink composition may also contain dyes other than pigments. Examples of dyes include acid dyes, reactive dyes, and direct dyes.

[0084] 1.1.4.2 Resin particles

[0085] The ink composition used in the recording method according to this embodiment contains resin particles. Resin particles are particles containing resin, also referred to as "resin dispersion" or "resin emulsion".

[0086] Examples of resins include, for example, urethane resins, polycarbonate resins, (meth)acrylic resins, styrene resins, silicone resins, styrene-acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins. These resins can be used alone or in combination of two or more.

[0087] Among these, the resin particles are preferably urethane resin, polycarbonate resin, (meth)acrylic resin, or styrene resin, more preferably urethane resin and (meth)acrylic resin, and even more preferably urethane resin. In particular, by making the resin particles urethane resin, the crosslinking agent contained in the treatment liquid described later can react with the urethane resin, thereby improving the color development, rubbing fastness, and penetration. Furthermore, it is presumed that in the above reaction, the crosslinking agent reacts with the OH groups that may be present in the urethane resin, but it is not limited thereto.

[0088] Urea resin is a resin containing urethane bonds within its molecule. From the viewpoint of ink preservation stability, anionic urethane resins with anionic functional groups such as carboxyl, sulfonyl, and hydroxyl groups are preferred.

[0089] Examples of urethane resins include polyether-type urethane resins whose main chain contains ether bonds in addition to urethane bonds, polyester-type urethane resins whose main chain contains ester bonds, and polycarbonate-type urethane resins whose main chain contains carbonate bonds. These urethane resins can be used in various combinations.

[0090] Commercially available urethane resins include ETERNACOLL UW-1501F, UW-1527F, UW-5002 (all manufactured by Ube Industries), Takelac WS-5000, W-6061, W-6110, WS-5984, WS-5100 (manufactured by Mitsui Chemicals), Permarin UA-150, UA-200, U-Coat UX-390 (manufactured by Sanyo Chemical Industries), and Hydran WLS-210 (manufactured by DIC).

[0091] Polycarbonate resin is a resin with polycarbonate bonds within its molecules. When urethane resin is not used, polycarbonate resin is preferred as a substitute.

[0092] Commercially available (meth)acrylic resins include Mowinyl 966A and 6760 (trade names manufactured by Nippon Synthetic Chemical Co., Ltd.).

[0093] (Meth)acrylic resin refers to a resin having a (meth)acrylic acid backbone. While not specifically limited to (meth)acrylic resin, examples include polymers of (meth)acrylic acid monomers such as (meth)acrylic acid and (meth)acrylic esters, and copolymers of (meth)acrylic acid monomers with other monomers. Examples of other monomers include vinyl monomers such as styrene. Furthermore, in this specification, the concept of "(meth)acrylic acid" includes both "methacrylic acid" and "acrylic acid".

[0094] Commercially available silicone resins include POLON-MF014, POLON-MF-18T, POLON-MF-33, KM-2002-T (these are trade names manufactured by Shin-Etsu Silicone Co., Ltd.), WACKER FINISH WR1100, NP2406, POWERSOFT FE 55, and TS2406 (these are trade names manufactured by Asahi Kasei Corporation).

[0095] The acid value of the resin contained in the resin particles is not particularly limited, but it is preferably 1 to 300 mg / g of KOH, more preferably 10 to 200 mg / g of KOH, and even more preferably 20 to 100 mg / g of KOH.

[0096] The content of resin particles relative to the total amount of the ink composition, in terms of solid content, is preferably 1.0% by mass or more, more preferably 2.0 to 20% by mass, and even more preferably 3.0 to 10% by mass. By keeping the content of resin particles within the above range, there is a tendency to obtain a recording material with excellent color development and excellent rubbing fastness.

[0097] 1.1.4.3 Water

[0098] The ink composition used in the recording method according to this embodiment may also contain water. The water used may be the same as that contained in the processing liquid described later, and the content may also be the same.

[0099] 1.1.4.4 Organic solvents

[0100] The ink composition used in the recording method according to this embodiment may also contain an organic solvent. As such an organic solvent, the same organic solvent that may be contained in the processing liquid described later can be used.

[0101] The ink composition preferably contains an organic solvent with a standard boiling point exceeding 280°C. Examples of organic solvents with a standard boiling point exceeding 280°C include glycerol and polyethylene glycol monomethyl ether, with glycerol being more preferred. The lower limit of the content of the organic solvent with a standard boiling point exceeding 280°C is preferably 1% by mass or more relative to the total amount of the ink composition, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 7% by mass or more. The upper limit of the content of the organic solvent with a standard boiling point exceeding 280°C is preferably 30% by mass or less relative to the total amount of the ink composition, more preferably 25% by mass or less, particularly preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0102] The lower limit of the organic solvent content is preferably 1% by mass or more relative to the total amount of the ink composition, more preferably 5% by mass or more, further preferably 10% by mass or more, and especially preferably 15% by mass or more. The upper limit of the organic solvent content is preferably 40% by mass or less relative to the total amount of the ink composition, more preferably 35% by mass or less, especially preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0103] 1.1.4.5 Surfactants

[0104] The ink composition used in the recording method according to this embodiment may also contain a surfactant. As such a surfactant, the same surfactant that may be contained in the processing liquid described later can be used, and the content can also be the same.

[0105] 1.1.4.6 pH Adjuster

[0106] The ink composition used in the recording method according to this embodiment may also contain a pH adjuster. There are no particular limitations on the pH adjuster; suitable combinations of acids, bases, weak acids, and weak bases can be listed. Examples of acids and bases used in such combinations include: as inorganic acids, sulfuric acid, hydrochloric acid, nitric acid, etc.; as inorganic bases, lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonia, etc.; as organic bases, triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, tris(hydroxymethyl)aminomethane (THAM), etc.; and as organic acids, adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (B... Good's buffer, phosphate buffer, citrate buffer, Tris buffer, etc., are available in various formulations including ES, 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), ethanolamine hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamidoglycine, tris(hydroxymethyl)methylglycine, glycineamide, N,N-dihydroxyethylglycine, etc.

[0107] The ink composition may use one pH adjuster alone or in combination with two or more. Furthermore, when using a pH adjuster, the total content relative to the total mass of the ink composition is, for example, 0.05% by mass or more and 3.0% by mass or less, more preferably 0.1% by mass or more and 1.0% by mass or less.

[0108] 1.1.4.7 Other ingredients

[0109] The ink composition used in the recording method according to this embodiment may also appropriately contain various additives other than those described above, such as lubricants, softeners, cosolvents, viscosity modifiers, humectants such as glycerol, antioxidants, preservatives / mildew inhibitors such as ProxelXL2 (trade name manufactured by Arch Chemicals), corrosion inhibitors, and chelating agents (e.g., sodium ethylenediaminetetraacetate) for capturing metal ions that affect dispersion. The organic solvents described above also include components such as glycerol, which are also organic solvents as mentioned above.

[0110] 1.1.4.8 Manufacturing and physical properties of ink compositions

[0111] The ink composition used in the recording method according to this embodiment can be obtained by mixing the above-mentioned components in any order and removing impurities by filtration or other methods as needed. As a method for mixing the components, it is preferable to use a method in which the materials are added sequentially and mixed by stirring in a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer.

[0112] From the viewpoint of reliability when using inkjet printing, it is preferable that the surface tension of the ink composition used in the recording method according to this embodiment is 20 to 40 mN / m, more preferably 22 to 35 mN / m. Furthermore, from the same viewpoint, it is preferable that the viscosity of the ink composition at 20°C is 1.5 to 10 mPa·s, more preferably 8 mPa·s or less, and even more preferably 2 to 8 mPa·s. To ensure that the surface tension and viscosity are within the aforementioned ranges, the types of organic solvents and surfactants, and the amounts of these and water added, can be appropriately adjusted.

[0113] 1.2 Processing liquid adhesion procedure

[0114] The recording method described in this embodiment includes a treatment liquid adhesion step, in which droplets of a treatment liquid containing a crosslinking agent are adhered to the fabric.

[0115] 1.2.1 Droplet weight of the treatment solution

[0116] In the recording method of this embodiment, the maximum weight of each droplet of the processing liquid is 30 ng or less, and the weight of the processing liquid droplets is less than or equal to the weight of the ink composition described above.

[0117] The maximum weight of each droplet of the preferred treatment solution is 27 ng or less, more preferably 24 ng or less, further preferably 21 ng or less, even more preferably 18 ng or less, particularly preferably 15 ng or less, and even more preferably 12 ng or less. The lower limit of the maximum weight of each droplet of the treatment solution is not particularly limited, but it is preferably 1 ng or more, more preferably 4 ng or more, further preferably 7 ng or more, and particularly preferably 10 ng or more. When the maximum weight of each droplet of the treatment solution is within the above-mentioned range, especially 11 ng, the ink and the treatment solution are more easily mixed, and sometimes the color development and rubbing fastness are further improved.

[0118] As described above, the droplet weight of the treatment liquid is less than or equal to the droplet weight of the ink composition, and preferably the droplet weight of the treatment liquid is smaller than the droplet weight of the ink composition.

[0119] In addition, the amount of treatment liquid adhering to the fabric is preferably 10 to 21 mg / inch per unit area of ​​the recording area. 2 More preferably 12–20 mg / inch 2More preferably 14–19 mg / inch 2 Especially preferred is 15–18 mg / inch 2 .

[0120] 1.2.2 Process Interval

[0121] As described above, in the recording method of this embodiment, it is preferable that the time difference between the ink adhesion step and the treatment liquid adhesion step is within 5 seconds. The preferred time difference in the case of alternating spraying with the treatment liquid sprayed first is as described above, and will not be explained further.

[0122] 1.2.3 Adhesion Method

[0123] As described above, the preferred recording method in this embodiment is alternating spraying, but it can also be a method of spraying first or using a line-type inkjet head to perform the ink adhesion process and the treatment liquid adhesion process.

[0124] 1.2.4 Treatment fluid

[0125] The processing liquid used in the recording method according to this embodiment contains a crosslinking agent. Hereinafter, the components contained in the processing liquid used in the recording method according to this embodiment will be described.

[0126] Furthermore, the treatment liquid is an auxiliary liquid used with the aforementioned ink composition for coloring fabrics, rather than the aforementioned ink composition itself. Additionally, it is preferable that the treatment liquid can cause the components of the ink composition to coagulate or thicken, and more preferably it contains components that cause the components of the ink composition to coagulate or thicken. The treatment liquid may also contain the aforementioned colorant, but the amount is preferably 0.2% by mass or less relative to the total amount of the treatment liquid, more preferably 0.1% by mass or less, further preferably 0.05% by mass or less, with a lower limit of 0% by mass. Preferably, the treatment liquid does not contain colorant.

[0127] 1.2.4.1 Crosslinking agent

[0128] The processing liquid used in the recording method according to this embodiment contains a crosslinking agent. As a crosslinking agent, any compound having crosslinking groups and capable of undergoing a crosslinking reaction can be used; known crosslinking agents can be employed. Preferably, a crosslinking agent that reacts with hydroxyl groups is preferred. With such a crosslinking agent, a crosslinking reaction can occur with the hydroxyl groups present in the resin particles contained in the ink composition, thereby making the ink easier to thicken / coagulate, further improving color development, and toughening the ink layer due to resin crosslinking, resulting in better rubbing fastness. Furthermore, when the fabric is cotton or the like, the crosslinking agent that reacts with hydroxyl groups undergoes a crosslinking reaction with the hydroxyl groups of cotton cellulose, thereby further improving the adhesion between the fabric and the ink layer, resulting in better rubbing fastness.

[0129] Furthermore, a cationic crosslinking agent is preferred. If the crosslinking agent is cationic, it can cause the anionic components (typically pigments, resin particles, etc.) in the ink composition to aggregate. This further improves the color development.

[0130] As a crosslinking agent, it is preferably selected from one or more of polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, melamine resin, and end-capped isocyanate resin. Among these, polyamide epichlorohydrin resin is more preferred as the crosslinking agent. When such a crosslinking agent is used, there is a tendency for better rubbing fastness and color development.

[0131] Polyamide epichlorohydrin resins are polymers obtained, for example, by an addition reaction of polyamide with epichlorohydrin or by polymerization of monomers containing amines, carboxylic acids, and epichlorohydrin. Furthermore, polyamide epichlorohydrin resins are considered to comprise polyamide polyamine-epoxychlorohydrin copolymers. Commercially available polyamide epichlorohydrin resins include Kymene 557 (manufactured by SOLENIS), WS-4020, 4030, 4027, TS-4070 (manufactured by Starlight PMC), AF-100, 251S, 255, 255LOX, and 2500 (manufactured by Arakawa Industrial Chemicals). These are cationic crosslinking agents.

[0132] Polyamine epichlorohydrin resins are polymers obtained, for example, by an addition reaction of a polyamine with epichlorohydrin, or by polymerization of monomers containing amines such as dimethylamine and epichlorohydrin. Commercially available examples of polyamine epichlorohydrin resins include Unisence KHE107L (manufactured by Yoka Co., Ltd.) and WS-4011 (manufactured by Hoshikatsu PMC Co., Ltd.). These are cationic crosslinking agents.

[0133] Examples of melamine resins include butylated melamine and fully etherified melamine. Water-soluble melamine resins are preferred. Commercially available melamine resins include Milliogen P-20 (manufactured by Yoka Co., Ltd.) and Sumirez Resin 8% AC (manufactured by Taoka Chemical Co., Ltd.). These are cationic crosslinking agents.

[0134] End-capped isocyanate resins are resins having isocyanate groups passivated by end-capping agents. When end-capped isocyanate resins are heated to a temperature above the crosslinking reaction initiation temperature, they react with hydroxyl groups present in the resin particles to form urethane bonds. This is because the end-capping agent that passivates the isocyanate groups of the end-capped isocyanate resin dissociates upon heating to a specified temperature, thereby activating the isocyanate groups and initiating the crosslinking reaction. As end-capped isocyanate resins, resins obtained by end-capping with TMP (trimethylolpropane) adducts or isocyanurates of HDI (hexamethylene diisocyanate), H6XDI (hydrogenated diphenylmethylene diisocyanate), IPDI (isophorone diisocyanate), or H12MDI (dicyclohexylmethane diisocyanate) are preferred. Commercially available products that are end-capped isocyanate resins include fixatives such as #220 (manufactured by Murayama Chemical Co., Ltd.), SU-268A (manufactured by Myojo Chemical Co., Ltd.), and MF-B60B (manufactured by Asahi Kasei Corporation).

[0135] The mass-average molecular weight of the crosslinking agent is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, particularly preferably 40,000 or less, and even more preferably 20,000 or less. The lower limit of the mass-average molecular weight of the crosslinking agent is not particularly limited, but it is preferably 100 or more, more preferably 1,000 or more, and even more preferably 5,000 or more. If the mass-average molecular weight of the crosslinking agent is 100,000 or less, there is a tendency to improve the spraying performance when coating the treatment liquid using inkjet printing. Furthermore, the mass-average molecular weight can be determined using gel permeation chromatography (GPC) with polyethylene glycol as the standard polymer.

[0136] The content of the crosslinking agent relative to the total amount of the treatment liquid is preferably 1 to 10% by mass, more preferably 3 to 9% by mass, even more preferably 4 to 8% by mass, particularly preferably 5 to 7% by mass, and even more preferably 6 to 7% by mass. If the content of the crosslinking agent is within the above range, there is a tendency to achieve a better balance between printing quality such as rubbing fastness, color development, and ink penetration, and the ejection performance when coating the treatment liquid using an inkjet method.

[0137] 1.2.4.2 Polyvalent Metal Salts

[0138] The processing liquid used in the recording method according to this embodiment preferably further contains a polyvalent metal salt. Polyvalent metal salts exhibit excellent reactivity with components in the ink, and by using them in conjunction with the aforementioned crosslinking agent, color development can be further improved.

[0139] As polyvalent metal salts, they are water-soluble compounds composed of divalent or higher-valent polyvalent metal ions and anions bonded to these polyvalent metal ions. Specific examples of polyvalent metal ions include Ca... 2+ Cu 2+ Ni 2+Mg 2 + Zn 2+ Ba2 + Divalent metal ions; Al 3+ Fe 3+ Cr 3+ Trivalent metal ions. Examples of anions include Cl-. - I - ,Br - SO4 2- ,ClO 3- NO 3- and HCOO - CH3COO - Among these polyvalent metal salts, calcium salts and magnesium salts are preferred from the viewpoint of the stability of the treatment solution and the reactivity as a coagulant, and magnesium salts are more preferred from the viewpoint of the balance between reactivity and frictional fastness.

[0140] When polyvalent metal salts are present, the lower limit of the polyvalent metal salt content relative to the total amount of the treatment solution is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 2.0% by mass or more. Furthermore, the upper limit of the polyvalent metal salt content relative to the total amount of the treatment solution is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0141] 1.2.4.3 Other coagulants

[0142] In addition to the crosslinking agent and polyvalent metal salts mentioned above, the processing liquid used in the recording method according to this embodiment may also contain components that cause the ink composition to coagulate or thicken. Examples of such components include organic acids and non-crosslinking cationic resins.

[0143] Examples of preferred organic acids include, for example, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid, pyranone carboxylic acid, pyrrolic carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof. An organic acid may be used alone or in combination of two or more. Furthermore, polyvalent metal salts may contain salts of organic acids that are also polyvalent metal salts.

[0144] Examples of cationic resins include cationic urethane resins, cationic olefin resins, and cationic amine resins. Any cationic amine resin containing an amino group is acceptable; examples include allylamine resins, polyamine resins, quaternary ammonium salt polymers, and polyamide resins. However, these resins, unlike the aforementioned crosslinking agents, do not possess crosslinking groups. Examples of polyamine resins include those containing an amino group in their main resin backbone. Examples of allylamine resins include those with a structure derived from an allyl group in their main resin backbone. Examples of quaternary ammonium salt polymers include those containing a quaternary ammonium salt in their structure. Examples of polyamide resins include those containing an amide group in their main resin backbone and an amino group in their side chains. Among cationic resins, cationic amine resins are preferred because they not only exhibit excellent reactivity but are also readily available.

[0145] 1.2.4.4 Water

[0146] The processing liquid used in the recording method according to this embodiment may also contain water. Examples of water include pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, and distilled water, as well as water with reduced ionic impurities such as ultrapure water. In addition, if water that has been sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is used, the growth of bacteria and fungi can be suppressed when the processing liquid is stored for a long time.

[0147] The water content relative to the total amount of the treatment liquid is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, even more preferably 50% by mass or more, particularly preferably 55% by mass or more, and even more preferably 60% by mass or more. By keeping the water content within the above range, the viscosity of the treatment liquid can be kept low. In addition, the upper limit of the water content relative to the total amount of the treatment liquid is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0148] 1.2.4.5 Organic solvents

[0149] The processing liquid used in the recording method described in this embodiment may also contain an organic solvent. Furthermore, it is preferred that the organic solvent be a water-soluble solvent. Water solubility means that after mixing water and the organic solvent at a 1:1 mass ratio at room temperature and stirring, a cloudy state cannot be confirmed as separation.

[0150] Examples of organic solvents include esters, alkylene glycol ethers, cyclic esters, nitrogen-containing solvents, and polyols. Examples of nitrogen-containing solvents include cyclic amides and non-cyclic amides. Examples of non-cyclic amides include alkoxyalkylamides.

[0151] As esters, examples include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, methoxybutyl acetate, and other ethylene glycol monoacetate esters; and diol diacetate esters, including ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol butyl acetate, diethylene glycol butyl acetate, diethylene glycol acetate propionate, diethylene glycol acetate propionate, dipropylene glycol acetate propionate, dipropylene glycol acetate butyl ester, dipropylene glycol acetate propionate, and other diol diacetate esters.

[0152] As alkylene glycol ethers, any mono- or di-ether of an alkylene glycol is acceptable, with alkyl ethers being preferred. Specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether (BTG), tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monobutyl ether, etc., which are alkylene glycol monoethyl ethers. Alkyl ethers; and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether.

[0153] Examples of cyclic esters include β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, β-heptanelactone, γ-heptanelactone, δ-heptanelactone, ε-heptanelactone, γ-octanelactone, δ-octanelactone, ε-octanelactone, δ-nonanolactone, ε-nonanolactone, and ε-decanolactone, as well as compounds in which the hydrogen atom of the methylene group adjacent to these carbonyl groups is replaced by an alkyl group having 1 to 4 carbon atoms.

[0154] Examples of alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, and 3-n-butoxy-N,N-methylpropionamide. Ethylpropionamide, 3-n-propoxy-N,N-dimethylpropionamide, 3-n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-isopropoxy-N,N-dimethylpropionamide, 3-isopropoxy-N,N-diethylpropionamide, 3-isopropoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3-tert-butoxy-N,N-methylethylpropionamide, etc.

[0155] As cyclic amides, examples include lactams, such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, and other pyrrolidones.

[0156] Examples of polyols include 1,2-alkanediols (e.g., ethylene glycol, propylene glycol (also known as propane-1,2-diol), 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, etc.) and polyols other than 1,2-alkanediols (polyhydroxy alcohols) (e.g., diethylene glycol, dipropylene glycol, triethylene glycol (TEG), 1,3-propanediol, 1,3-butanediol). (Alcohols), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, trimethylolpropane, glycerol, etc.

[0157] Organic solvents can be used alone or in combination of two or more.

[0158] The processing solution preferably contains an organic solvent with a standard boiling point exceeding 280°C, one of the organic solvents exemplified above. Examples of organic solvents with a standard boiling point exceeding 280°C include glycerol and polyethylene glycol monomethyl ether, with glycerol being more preferred. The lower limit of the content of the organic solvent with a standard boiling point exceeding 280°C relative to the total amount of the processing solution is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more. The upper limit of the content of the organic solvent with a standard boiling point exceeding 280°C relative to the total amount of the processing solution is preferably 40% by mass or less, more preferably 35% by mass or less, particularly preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0159] The lower limit of the organic solvent content relative to the total amount of the treatment liquid is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more. The upper limit of the organic solvent content relative to the total amount of the treatment liquid is preferably 40% by mass or less, more preferably 35% by mass or less, particularly preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0160] 1.2.4.6 Surfactants

[0161] The processing liquid used in the recording method according to this embodiment may also contain a surfactant. There are no particular limitations on the surfactant; examples include acetylenic diol surfactants, fluorinated surfactants, and organosilicon surfactants. It is preferable to contain at least one of these, and more preferably, an acetylenic diol surfactant.

[0162] As an alkynyl diol surfactant, there are no particular limitations, but examples include Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, and DF110D (all trade names, Air Products). Olfine B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nisshin Chemical Industry Co., Ltd.), Acetylenol E00, E00P, E40, E100 (all trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0163] There are no particular limitations on the organosilicon surfactant, but polysiloxane compounds are preferred. There are no particular limitations on the polysiloxane compound, but polyether-modified organosilicon compounds are examples. Commercially available products of this polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (trade names, manufactured by BYK Chemie Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (trade names, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

[0164] As a fluorinated surfactant, fluorinated modified polymers are preferred. For example, BYK-340 (trade name, manufactured by BYK Chemie Co., Ltd., Japan) can be cited.

[0165] When a surfactant is present, its content relative to the total amount of the treatment liquid can be 0.1% by mass or more and 1.5% by mass or less, preferably 0.5% by mass or more and 1% by mass or less.

[0166] 1.2.4.7 Preservatives / Mold Inhibitors

[0167] The processing liquid used in the recording method described in this embodiment may also contain preservatives / mildew inhibitors. Examples of preservatives / mildew inhibitors include sodium benzoate, sodium pentachlorophenolate, sodium 2-pyridinium-1-oxide, sodium sorbate, sodium dehydroacetate, Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel IB, and Proxel TN (all manufactured by Lonza Japan, trade names), and 4-chloro-3-methylphenol (such as Preventol CMK from Bayer).

[0168] When preservatives / mildew inhibitors are present, their content relative to the total amount of the treatment liquid can be, for example, 0.05% by mass or more and 1.0% by mass or less, preferably 0.1% by mass or more and 0.5% by mass or less.

[0169] 1.2.4.8 Other ingredients

[0170] The processing liquid used in the recording method according to this embodiment may also appropriately contain various additives other than those mentioned above, such as softeners, solubilizers, viscosity modifiers, pH adjusters such as triethanolamine, humectants such as glycerol, antioxidants, corrosion inhibitors, and chelating agents (e.g., sodium ethylenediaminetetraacetate) for capturing metal ions that affect dispersion. The organic solvents mentioned above also include components such as glycerol, which is also an organic solvent as described above.

[0171] 1.2.4.9 Manufacturing and physical properties of the treatment fluid

[0172] The processing liquid used in the recording method according to this embodiment can be obtained by mixing the above-mentioned components in any order and removing impurities by filtration or other methods as needed. As a method for mixing the components, it is preferable to use a method in which the materials are added sequentially and mixed by stirring in a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer.

[0173] From the viewpoint of reliability when using inkjet printing, it is preferable that the surface tension of the processing liquid used in the recording method according to this embodiment is 20 to 40 mN / m, more preferably 22 to 35 mN / m. Furthermore, from the same viewpoint, it is preferable that the viscosity of the processing liquid at 20°C is 1.5 to 10 mPa·s, more preferably 8 mPa·s or less, and even more preferably 2 to 8 mPa·s. To ensure that the surface tension and viscosity are within the aforementioned ranges, the types of organic solvents and surfactants, and the amounts of these and water added, can be appropriately adjusted.

[0174] 1.3 Other processes

[0175] The recording method described in this embodiment may include a step of heating the ink or the like adhered to the fabric after the ink adhesion step and the processing liquid adhesion step described above. The heating method is not particularly limited, but examples include hot pressing, atmospheric pressure steam method, high pressure steam method, and thermosetting method. The heat source is not particularly limited, but examples include infrared lamps. The heating temperature is preferably the temperature at which the resin particles of the ink melt and the medium such as water evaporates. For example, it is preferably about 100°C or higher and about 200°C or lower, more preferably 170°C or lower, and even more preferably 160°C or lower. Here, the heating temperature in the heating step refers to the surface temperature of the image or the like formed on the fabric. The heating time is not particularly limited, but for example, it is 30 seconds or more and 20 minutes or less.

[0176] Following the heating process, there may also be a process of washing and drying the printed fabric. During the washing process, hot soap solution or similar liquid can be used to rinse away ink and other components that are not fixed to the fabric as a soaping treatment, if necessary.

[0177] 1.4 Inkjet Printing Equipment

[0178] While referring to Figure 1 One example is an inkjet printing apparatus with an inkjet head that can be applied to the recording method involved in this embodiment.

[0179] Furthermore, the inkjet printing apparatus used in the following description is a serial printer, in which a recording inkjet head is mounted on a carriage that moves in a predetermined direction, and the inkjet head moves with the carriage, thereby spraying droplets onto the fabric. The inkjet printing apparatus suitable for the recording method described in this embodiment is not limited to a serial printer, but can also be a line printer. A line printer is a printer in which the inkjet head is formed to be wider than the width of the fabric, and sprays droplets onto the fabric in a manner that does not cause the inkjet head to move.

[0180] Inkjet printing and dyeing equipment is a device that prints and dyes fabric by causing droplets to fall onto the fabric through an inkjet head, which is a liquid ejector that ejects tiny droplets of ink composition and processing liquid. Figure 1 This is a schematic perspective view showing the inkjet printing apparatus used in the embodiment.

[0181] like Figure 1 As shown, in this embodiment, the printer 1 includes an inkjet head 3, a carriage 4, a main scanning mechanism 5, a paper pressure roller 6, and a control unit (not shown) that controls the overall operation of the printer 1. The inkjet head 3 is mounted on the carriage 4, and liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f that can be detachably installed and stored to hold the ink composition and processing liquid supplied to the inkjet head 3.

[0182] The main scanning mechanism 5 includes: a timing belt 8 connected to the carriage 4; a motor 9 driving the timing belt 8; and a guide shaft 10. The guide shaft 10 serves as a support component for the carriage 4 and is mounted on the scanning direction of the carriage 4, i.e., the main scanning direction MS. The carriage 4 is driven by the motor 9 via the timing belt 8 and can reciprocate along the guide shaft 10. Thus, the main scanning mechanism 5 has the function of reciprocating the carriage 4 in the main scanning direction MS.

[0183] The pressure roller 6 has the function of conveying the fabric 2 to be printed in the secondary scanning direction SS, which is orthogonal to the main scanning direction MS, i.e., the length direction of the fabric 2. Thus, the fabric 2 is conveyed along the secondary scanning direction SS. The carriage 4, which carries the inkjet head 3, can reciprocate in the main scanning direction MS, which is approximately the same as the width direction of the fabric 2. The inkjet head 3 is configured to scan relative to the fabric 2 in both the main scanning direction MS and the secondary scanning direction SS.

[0184] Liquid containers 7a, 7b, 7c, 7d, 7e, and 7f are six independent liquid containers. Liquid containers 7a, 7b, 7c, 7d, 7e, and 7f can hold the ink composition and processing liquid used in the recording method according to this embodiment. These liquid containers respectively hold ink compositions and processing liquids in colors such as black, cyan, magenta, yellow, white, and orange, which can be used in any combination. Figure 1 In this design, the number of liquid cartridges is set to six, but is not limited to this. At the bottom of liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f, there are supply ports (not shown) for supplying the ink composition or processing liquid contained in each liquid cartridge to the inkjet head 3.

[0185] The inkjet head 3, under the control of a control unit (not shown), sprays ink compositions and processing liquids supplied from liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f from multiple nozzles onto the fabric 2, causing it to adhere. The inkjet head 3 has multiple nozzles on the side opposite the fabric 2 to which the ink compositions and processing liquids are adhered. These multiple nozzles are arranged in a row to form a nozzle array, each nozzle array corresponding to a different color ink composition and processing liquid. The different color ink compositions and processing liquids are supplied from each liquid cartridge to the inkjet head 3 and ejected as droplets from the nozzles via actuators (not shown) within the inkjet head 3. The ejected droplets of ink compositions and processing liquids fall onto the fabric 2, forming images, text, patterns, colors, etc., on the printing area of ​​the fabric 2, achieved through the adhesion treatment relative to the fabric 2 and the ink. Furthermore, multiple inkjet heads 3 may be provided on a carriage 4.

[0186] Here, a piezoelectric element is used as an actuator in the inkjet head 3 as a driving means, but it is not limited to this method. For example, an electromechanical conversion element that displaces the vibrating plate as an actuator by electrostatic adsorption can also be used, or an electrothermal conversion element that uses bubbles generated by heating to eject the ink composition as droplets can also be used.

[0187] The inkjet head 3 includes: a nozzle group for ejecting processing liquid; and a nozzle group for ejecting ink composition. The ejected nozzle group refers to the nozzle group used for recording in the recording method. It is a group of nozzles that eject ink or the like from the nozzles if an image should be recorded on an area of ​​fabric opposite the nozzle group during the main scan, and is a continuous nozzle group in the sub-scanning direction SS. Therefore, although the nozzle group itself exists, nozzle groups not used for recording in the recording method are not included in the ejected nozzle group.

[0188] Figure 2 , Figure 3 and Figure 4 An example of the configuration of the inkjet head 3 is shown. Figure 2The inkjet heads 3a and 3b are arranged from the upstream side toward the downstream side in the transport direction (sub-scanning direction SS). Additionally, in Figure 3 In the middle, inkjet heads 3a and 3b are located at the same position in the sub-scanning direction SS and are arranged side by side. Additionally, in Figure 4 In the middle, the inkjet heads 3a and 3b are arranged in such a way that they have overlapping parts and are arranged from the upstream side to the downstream side in the transport direction (sub-scanning direction SS).

[0189] In the recording method of this embodiment, it is preferable that the inkjet head 3 has a processing liquid nozzle group for recording located upstream of or overlapping with the nozzle group for recording the ink composition in the fabric transport direction. Furthermore, from the same viewpoint, it is preferable that the head ejecting the processing liquid is located at the same position as the head ejecting the ink composition in the fabric transport direction, or upstream of the head ejecting the ink composition in the fabric transport direction. With such a structure, droplets can adhere by alternating spraying, with the processing liquid being sprayed first, making it easier for the components of the ink composition and the processing liquid to mix and for the reaction to proceed easily. Therefore, there is a tendency for superior color development, rubbing fastness, and bleed suppression.

[0190] For example, in Figure 2 In this example, by setting inkjet head 3a as the head that ejects the processing liquid and inkjet head 3b as the head that ejects the ink composition, the processing liquid nozzle assembly for recording can be positioned upstream of the ink composition nozzle assembly in the fabric transport direction (sub-scanning direction SS). In this case, the processing liquid adheres to the fabric before the ink composition. That is, the processing liquid can be ejected first to form a layer containing the processing liquid, and then a layer containing the ink composition can be formed in a stacked manner.

[0191] For example, in Figure 3 In the example, when inkjet head 3a is configured to eject the processing liquid and inkjet head 3b is configured to eject the ink composition, and the nozzle group for the processing liquid for recording overlaps with the nozzle group for the ink composition for recording, alternating ejection is possible. That is, alternating and repeated layering of the processing liquid and the ink composition is possible (layering like a mille-feuille cake).

[0192] Furthermore, the "overlapping portion" refers to the portion of the nozzle assembly for recording the ink composition and the nozzle assembly for recording the processing liquid that is located at the same position in the sub-scanning direction SS. Thus, the ink composition and processing liquid overlap and adhere to the fabric through the same main scan.

[0193] For example, in Figure 4In the example, when inkjet head 3a is configured to eject the processing liquid and inkjet head 3b is configured to eject the ink composition, and both have overlapping portions between the processing liquid nozzle group and the ink composition nozzle group for recording, alternating ejection is possible. Alternatively, when inkjet head 3a is configured to eject the processing liquid and inkjet head 3b is configured to eject the ink composition, and both do not have overlapping portions between the processing liquid nozzle group and the ink composition nozzle group for recording, but the processing liquid nozzle group for recording is located upstream of the ink composition nozzle group in the fabric transport direction (sub-scanning direction SS), processing liquid ejection first is possible.

[0194] A drying mechanism and a heating mechanism (neither shown) can also be installed on printer 1. The drying and heating mechanisms are used to efficiently dry the processing liquid and ink adhering to the fabric 2. Their placement is not particularly limited, as long as they are located in a position capable of drying / heating the fabric 2. For example, to efficiently dry the ink and processing liquid adhering to the fabric 2, for example... Figure 1 In this configuration, the drying mechanism and the heating mechanism can be positioned opposite the inkjet head 3.

[0195] Examples of drying and heating mechanisms include a printer heater mechanism that heats the fabric 2 by contacting it with a heat source, a mechanism that irradiates with infrared light or electromagnetic waves with a maximum wavelength of around 2450 MHz (e.g., microwaves), and a drying mechanism that blows hot air. Heating of the fabric 2 occurs before or during the application of the ink droplets ejected from the nozzles of the inkjet head 3 to the fabric 2. Control of various heating conditions, such as the timing of heating, heating temperature, and heating time, is performed by a control unit.

[0196] Alternatively, the drying and heating mechanisms can be located downstream of the fabric 2 in the conveying direction. In this case, the fabric 2 is heated after the ink or processing liquid ejected from the nozzle adheres to the fabric 2 and forms an image. This improves the drying properties of the ink or processing liquid adhering to the fabric 2.

[0197] 2. Example

[0198] The present invention will be further described in detail below through examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" refers to the mass percentage.

[0199] 2.1 Preparation of the treatment solution

[0200] The components were placed in a container according to the compositions in Tables 1 and 2 below, mixed and stirred for 1 hour using a magnetic stirrer, and then filtered using an 8 μm PTFE membrane filter to obtain the treatment solutions involved in each example and comparative example. Pure water was added to bring the total volume of each treatment solution to 100% by mass. Furthermore, the values ​​for crosslinking agent and non-crosslinking agent in Tables 1 and 2 below are expressed as mass percentages of the solid components as active ingredients.

[0201]

[0202]

[0203] The records in Tables 1 and 2 above are explained in detail below.

[0204] Treatment liquid components

[0205] Crosslinking agent / non-crosslinking agent

[0206] • Crosslinking agent 1 (UnisenceKHE107L, trade name manufactured by a dyeing and chemical company, polyamine epichlorohydrin resin)

[0207] • Crosslinking agent 2 (Milliogen P-20, a trade name manufactured by a dyeing and chemical company, melamine resin)

[0208] • Crosslinking agent 3 (Kymene 557, trade name manufactured by SOLENIS, polyamide epichlorohydrin resin)

[0209] • Crosslinking agent 4 (Fixing agent #220, trade name manufactured by Murayama Chemical Co., Ltd., end-capped isocyanate resin)

[0210] • Cationic resin (EP-1137, a trade name manufactured by Takamatsu Oil Co., Ltd., a non-crosslinking cationic polymer)

[0211] Other solvents

[0212] • Surfactant (Olfine E1010, trade name manufactured by Nissin Chemical Industries, Inc., acetylenic diol surfactant)

[0213] • ProxelXL2 (product name manufactured by Lonza Japan, preservative / mildew inhibitor)

[0214] term

[0215] • "Processing liquid-ink ejection time difference": The time difference between the ink adhesion process and the processing liquid adhesion process, from the last ejection of the processing liquid to the initial ejection of the ink composition.

[0216] • "Number of passes": The number of main scans performed to allow the ink composition and processing liquid to adhere to the same area.

[0217] • "Processing liquid first": The processing liquid is sprayed first; through different main scans, the ink composition and processing liquid are adhered to the same scanning area of ​​the fabric, so that the layer containing the processing liquid is formed first, followed by the layer containing the ink composition being formed in layers.

[0218] • "Alternating": Alternating spraying; applying the ink composition and treatment liquid to the same scanned area of ​​the fabric through the same master scan, forming a layer containing the ink composition and treatment liquid.

[0219] 2.2 Preparation of Ink Composition

[0220] The components were placed in a container according to the composition in Table 3 below, mixed and stirred for 1 hour using a magnetic stirrer, and then filtered using an 8μm PTFE membrane filter to obtain the ink composition containing each ink component. Pure water was added to bring the total amount of each ink composition to 100% by mass.

[0221] In addition, for pigments, a pigment dispersion was prepared by mixing pigments with water in a mass ratio of pigment:pigment dispersant = 2:1 (not listed in the table) as a water-soluble resin based on styrene and acrylic acid, and stirring. This pigment dispersion was then used in the preparation of inks.

[0222] Table 3

[0223]

[0224] 2.3 Production of Printed and Dyed Materials

[0225] Using a modified PX-H8000 (manufactured by Seiko Epson Corporation) apparatus, printing was performed on a recording medium of 100% cotton white plain cloth or 100% polyester satin under the conditions described in Tables 1 and 2 above, forming a full-page pattern image on an A4-sized fabric as the recording medium. The printed materials involved in each embodiment and comparative example were then produced by heating them in an oven at 160°C for 3 minutes and then drying them. Furthermore, the inkjet head used a head unit with a nozzle spacing of 600 dpi and 600 nozzles in the width direction of the recording medium. Additionally, a "full-page pattern image" refers to an image formed by recording dots relative to all pixels of a pixel area that is the smallest recording unit area defined by the recording resolution (100% occupancy).

[0226] 2.4 Evaluation Methods

[0227] 2.4.1 Frictional fastness

[0228] The dyed and printed materials obtained above were subjected to a rubbing fastness test according to ISO 105-X12 test method. The wet rubbing fastness was evaluated according to the following criteria. A rubbing fastness of C or above can be considered good.

[0229] Evaluation Criteria

[0230] A++: Level 4-5 or above

[0231] A+: Level 4

[0232] A: Level 3-4

[0233] B: Level 3

[0234] C: Level 2-3 or higher but less than Level 3

[0235] D: Level 2 and below

[0236] 2.4.2 Hair color

[0237] The obtained printed and dyed materials were tested using a fluorescence spectrophotometer ("FD-7", manufactured by Konica Minolta) to determine the OD value of cyan, and the color development was evaluated according to the following criteria. A color development of C or above was considered to be good.

[0238] Evaluation Criteria

[0239] A+: OD value of 1.48 or higher

[0240] A: OD value is 1.45 or higher but less than 1.48

[0241] B: OD value above 1.40 but less than 1.45

[0242] C: OD value greater than 1.35 but less than 1.40

[0243] D: OD value less than 1.35

[0244] 2.4.3 Ejection Performance

[0245] The spraying performance of the treatment solution used in the "production of printed and dyed materials" was evaluated according to the following criteria. A spraying performance of B or higher is considered good.

[0246] Evaluation Criteria

[0247] A: The nozzle did not detach, and the printed surface was evenly printed without any spots.

[0248] B: The nozzles do not detach, and the printed surface is evenly dyed without any spots. If left for 2 hours, the nozzles will detach and require cleaning.

[0249] C: The nozzle has detached, and linear unprinted areas can be observed on the printed surface.

[0250] 2.4.4 Infiltration

[0251] In the evaluation of ink penetration, the same printing material used in the "rubbing fastness" test described above was employed. The uneven ink cohesion within the full-print pattern was visually observed, and the evaluation was conducted according to the following criteria. A result of B or higher is considered a good result.

[0252] Evaluation Criteria

[0253] A: No uneven agglomeration was found within the full-page pattern.

[0254] B: Some unevenness in cohesion was observed within the full-page pattern.

[0255] C: A considerable amount of uneven cohesion was found throughout the full-page pattern.

[0256] 2.5 Evaluation Results

[0257] The evaluation results are shown in Tables 1 and 2 above.

[0258] According to Tables 1 and 2 above, the recording method relative to the fabric includes: an ink adhesion step, in which droplets of an ink composition containing pigment and resin particles are adhered to the fabric; and a treatment liquid adhesion step, in which droplets of a treatment liquid containing a crosslinking agent are adhered to the fabric, wherein the maximum weight of each droplet of the ink composition is 30 ng or less, the maximum weight of each droplet of the treatment liquid is 30 ng or less, the weight of the treatment liquid droplets is less than the weight of the ink composition droplets, and the color development and rubbing fastness are excellent in the recording methods involved in each embodiment.

[0259] Based on the comparison of Examples 1-3 and Comparative Examples 1 and 2, if the treatment liquid contains a crosslinking agent that reacts with the resin particles in the ink, the rubbing fastness and color development are good.

[0260] Based on the comparison of Example 3 and Comparative Examples 3-6, the smaller the amount of processing liquid and ink ejected, and the smaller the amount of processing liquid ejected compared to ink, the better the printing quality.

[0261] More specifically, if the treatment solution is sprayed, the amount of adhesion increases and the amount of water also increases, making it easy to seep in, resulting in poor drying properties and a decrease in friction fastness (Comparative Example 3).

[0262] If the droplets are large, the treatment liquid and ink can easily penetrate into the fabric, resulting in less crosslinking near the surface. This is considered to reduce the effect of improving rubbing fastness and color development (Comparative Example 4).

[0263] If the ink spray size is large, it cannot be printed evenly, resulting in unevenness, reduced color development, and the resin particles cannot be evenly coated, thus reducing rubbing fastness (Comparative Example 5).

[0264] If the spray size of the treatment liquid is large, the crosslinking agent cannot be evenly coated, so the effect of improving friction adhesion is small. In addition, if the ink spray size is too small, the bleeding evaluation will be worse due to uneven airflow ripples (Comparative Example 6).

[0265] According to Examples 1-3, the good rubbing fastness and color development depend on the type of crosslinking agent, especially the high effect of crosslinking agent 3 on polyamide epichlorohydrin resin.

[0266] According to Examples 3 and 4, if the spraying time difference is long, the rubbing fastness and color development will decrease slightly. Therefore, a time difference of less than 5 seconds is preferred. This is believed to be because the pre-coated treatment liquid penetrates into the fabric, thus reducing the crosslinking dosage near the surface and decreasing the effect of improving rubbing fastness and color development.

[0267] According to Examples 3 and 5, the alternating spray side exhibited good rubbing fastness and color development. This is believed to be because by forming a layer containing ink and processing liquid, the processing liquid and ink form a layered structure, thereby facilitating the reaction between the crosslinking agent and the resin particles in the ink.

[0268] In Examples 5 and 6, the printing quality was essentially the same. Therefore, it is believed that as long as the time difference is within 5 seconds, the effects of improved rubbing adhesion and color development are sufficient.

[0269] According to Examples 6 and 7, if the amount of treatment liquid sprayed is smaller than that of ink, the rubbing adhesion and color development become even better. This is believed to be because by coating the treatment liquid into a fine powder, it can be evenly dispersed on the fabric surface, making it easier for it to react with the resin particles in the ink and the fabric.

[0270] According to Example 8, if the resin particles in the ink are replaced with resin particles that do not have OH groups, the quality decreases. This is believed to be because the crosslinking agent cannot react with the resin particles.

[0271] According to Example 9, if a non-cationic crosslinking agent is used, the color development and penetration decrease. Therefore, a cationic crosslinking agent is preferred.

[0272] According to Examples 7, 10, and 11, the higher the crosslinking dosage, the better the printing quality, but the inkjet ejection performance decreases.

[0273] According to Examples 7, 12, and 13, the color development is further improved by adding a polyvalent metal salt. Furthermore, depending on the type of polyvalent metal salt, sometimes excessive cohesion can lead to decreased frictional strength; therefore, MgSO4 is better than CaCl2.

[0274] According to Example 14, it can be seen that it is effective not only for 100% cotton fabrics, but also for fabrics made from various raw materials.

[0275] The following content can be derived from the above implementation method.

[0276] One method of recording is a method of recording relative to cloth, which has the following characteristics:

[0277] The ink adhesion process involves adhering droplets of an ink composition containing pigments and resin particles to the fabric; and

[0278] The treatment liquid adhesion process involves attaching droplets of a treatment liquid containing a crosslinking agent to the fabric.

[0279] The maximum weight of each droplet of the ink composition is less than 30 ng.

[0280] The maximum weight of each droplet of the treatment solution is less than 30 ng.

[0281] The droplet weight of the processing liquid is less than or equal to the droplet weight of the ink composition.

[0282] In one of the above recording methods, it can be:

[0283] The droplet weight of the treatment liquid is smaller than the droplet weight of the ink composition.

[0284] In any of the above recording methods, it can be:

[0285] The time difference between the ink adhesion process and the treatment liquid adhesion process is within 5 seconds.

[0286] In any of the above recording methods, it can be:

[0287] The treatment liquid adhesion process and the ink adhesion process are performed using inkjet printing.

[0288] In the inkjet method, a main scan is performed multiple times, in which the inkjet head moves in a direction perpendicular to the fabric transport direction to record data.

[0289] The processing liquid and the ink composition are adhered to the same scanned area of ​​the fabric by using the same master scan.

[0290] The same main scan is performed multiple times on the same scanning area.

[0291] In any of the above recording methods, it can be:

[0292] The crosslinking agent is a crosslinking agent that reacts with hydroxyl groups.

[0293] In any of the above recording methods, it can be:

[0294] The resin particles are urethane resin.

[0295] In any of the above recording methods, it can be:

[0296] The fabric contains hydroxyl groups.

[0297] In any of the above recording methods, it can be:

[0298] The crosslinking agent is selected from one or more of polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, melamine resin, and end-capped isocyanate resin.

[0299] In any of the above recording methods, it can be:

[0300] The crosslinking agent is cationic.

[0301] In any of the above recording methods, it can be:

[0302] The content of the crosslinking agent is 1 to 10% by mass relative to the total amount of the treatment liquid.

[0303] In any of the above recording methods, it can be:

[0304] The treatment solution further contains polyvalent metal salts.

[0305] In any of the above recording methods, it can be:

[0306] The inkjet head is configured to have a processing liquid nozzle group for recording on the upstream side of or overlapping with the nozzle group for recording ink composition in the transport direction of the fabric.

[0307] This invention is not limited to the embodiments described above and can be modified in various ways. For example, this invention includes structures that are substantially the same as those described in the embodiments, such as structures with the same function, method, and result, or structures with the same purpose and effect. Additionally, this invention includes structures that replace non-essential parts of the structures described in the embodiments. Furthermore, this invention includes structures that achieve the same effect as those described in the embodiments or structures that can achieve the same purpose. Additionally, this invention includes structures that incorporate known techniques into the structures described in the embodiments.

Claims

1. A recording method, characterized in that, The recording method, relative to recording on cloth, has the following characteristics: The ink adhesion process involves adhering droplets of an ink composition containing pigments and resin particles to the fabric. as well as The treatment liquid adhesion process involves attaching droplets of a treatment liquid containing a crosslinking agent to the fabric. The maximum weight of each droplet of the ink composition is less than 30 ng. The maximum weight of each droplet of the treatment solution is less than 30 ng. The droplet weight of the processing liquid is less than or equal to the droplet weight of the ink composition. The treatment liquid adhesion process and the ink adhesion process are performed using inkjet printing. In the inkjet method, a main scan is performed multiple times, in which the inkjet head moves in a direction perpendicular to the fabric transport direction to record data. The processing liquid and the ink composition are adhered to the same scanned area of ​​the fabric by using the same master scan. The same main scan is performed multiple times on the same scanning area.

2. The recording method according to claim 1, characterized in that, The droplet weight of the treatment liquid is smaller than the droplet weight of the ink composition.

3. The recording method according to claim 1 or 2, characterized in that, The time difference between the ink adhesion process and the treatment liquid adhesion process is within 5 seconds.

4. The recording method according to claim 1, characterized in that, The crosslinking agent is a crosslinking agent that reacts with hydroxyl groups.

5. The recording method according to claim 1, characterized in that, The resin particles are urethane resin.

6. The recording method according to claim 1, characterized in that, The fabric contains hydroxyl groups.

7. The recording method according to claim 1, characterized in that, The crosslinking agent is selected from one or more of polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, melamine resin, and end-capped isocyanate resin.

8. The recording method according to claim 1, characterized in that, The crosslinking agent is cationic.

9. The recording method according to claim 1, characterized in that, The content of the crosslinking agent is 1% to 10% by mass relative to the total amount of the treatment liquid.

10. The recording method according to claim 1, characterized in that, The treatment solution further contains polyvalent metal salts.

11. The recording method according to claim 1, characterized in that, The inkjet head is configured to have a processing liquid nozzle group for recording on the upstream side of the nozzle group for recording ink composition in the conveying direction of the fabric or in the portion overlapping with the nozzle group for recording ink composition.

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