JP2014208928A - Discharge printing agent, container, ink-jet recording apparatus, method for discharge printing, method for forming image, agent for stabilizing discharge printing agent, and method for stabilizing discharge printing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a discharge printing agent that enables at least one of improvement in discharge printing performance and long-term storage stabilization.SOLUTION: The present invention provides a discharge printing agent containing thiourea dioxide, wherein the discharge printing agent further contains at least one of the following components (i) and (ii): (i) at least one salt selected from the group consisting of a salt of monocarboxylic acid, a salt of ascorbic acid, and a salt of metasilicic acid; and (ii) β-diketone.

Description

  The present invention relates to a discharging agent, a container, an ink jet recording apparatus, a discharging method, an image forming method, a discharging agent stabilizer, and a discharging agent stabilization method.

  As a discharging agent used for discharging a fabric, a discharging agent containing Rongalite as a reducing agent is known (Patent Document 1). According to this discharging agent, a color image can be formed on a dark fabric by discharging the fabric by an oxidation-reduction reaction and forming an image using color ink at the discharging portion.

Japanese Patent Laid-Open No. 61-6365

  However, the above-described discharging agent containing Rongalite has been required to be used within a short period after preparation because, for example, the reducing power is lost in less than one day. Further, the discharging agent containing Rongalite described above has a weak discharging power, and even when color ink is used, an appropriate image may not be formed at the discharging portion.

  Therefore, an object of the present invention is to provide a discharging agent capable of at least one of improving the discharging power and stabilizing the storage over a long period of time.

In order to achieve the above object, the discharging agent of the present invention comprises:
A discharge agent containing thiourea dioxide,
Furthermore, it includes at least one of the following (i) and (ii).

(I) at least one salt selected from the group consisting of monocarboxylate, ascorbate and metasilicate (ii) β-diketone

  By including thiourea dioxide as a reducing agent and at least one of the above (i) and (ii), the discharging agent of the present invention can improve at least one of discharging power and stabilize the storage over a long period of time.

FIGS. 1A and 1B are diagrams showing application examples of a discharging agent in the discharging method of the present invention. FIG. 2 is a schematic diagram illustrating an example of the configuration of the ink jet recording apparatus. FIG. 3 is a front view showing an example of the configuration of the ink jet printer of the ink jet recording apparatus. FIG. 4A is a plan view showing a state in which a fabric is set on the platen of the ink jet recording apparatus, and FIG. 4B is a cross-sectional view seen from the AA direction of FIG. . FIG. 5 is a block diagram showing a configuration of the ink jet recording apparatus. FIG. 6 is a functional block diagram of the ink jet recording apparatus.

  The discharging agent of the present invention is used for discharging a fabric. Examples of the fabric include clothing such as T-shirts, swimwear, and trainers, bags, shoes, slippers, socks, furniture such as sofas, and fabric products such as flags. The fabric includes both woven fabric and knitted fabric. The material of the fabric is, for example, natural fiber from the viewpoint of discharging effect. Examples of the natural fiber include cotton and silk. The material of the fabric may be a mixed spinning in which a plurality of types of the fibers are mixed and spun. Note that “discharging” is different from bleaching usually performed at home or the like in the process and the target of action. Specifically, bleaching performed at home or the like involves immersing clothes in chemicals and chemically decomposing the soil itself by an oxidation reaction or a reduction reaction. On the other hand, “discharging” is to directly act on a dye molecule dyeing a fabric, particularly cotton fiber, to chemically decompose the molecule. Furthermore, the process of “discharging” includes, for example, a process in the presence of high-temperature steam such as heating the cloth to 100 ° C. or higher using an apparatus called a heat press in addition to immersing the fabric in a drug. Including. In the presence of such high-temperature steam, for example, thiourea dioxide (aminoiminomethanesulfinic acid), which is the main component, is decomposed, and as a result, sulfoxylic acid having reducing power is generated. A chemical reaction scheme in which this sulfoxylic acid acts on the dye molecule is presumed. However, this mechanism is speculation, and the present invention is not limited or limited by this speculation.

As described above, the discharge agent of the present invention is a discharge agent containing thiourea dioxide, and further includes at least one of the following (i) and (ii).

(I) at least one salt selected from the group consisting of monocarboxylate, ascorbate and metasilicate (ii) β-diketone

  The discharge agent of the present invention can be stored for a long period of time, for example, by using thiourea dioxide, which is a reducing agent, and at least one of the above (i) and (ii). Moreover, the discharge agent of this invention improves discharge power, for example by using together the thiourea dioxide which is a reducing agent, and said (i). When discharging with thiourea dioxide, the reaction intermediate is stabilized by the nucleophilic action of the carbonyl carbon, and the intermediate is decomposed over time, thus increasing the effective yield of sulfoxylic acid. As a result, it is estimated that the discharging effect is improved. However, this mechanism is speculation, and the present invention is not limited or limited by this speculation. Further, the above-described discharging agent containing Rongalite has a problem that formaldehyde is generated by decomposition of Rongalite. Formaldehyde has a very strong pungent odor, and the pungent odor may worsen the working environment or may remain in the product and cause odor. For this reason, depending on the working environment, it may be unfavorable to generate formaldehyde. On the other hand, the discharging agent of the present invention does not need to use Rongalite, and therefore does not generate formaldehyde. Furthermore, according to the discharge agent of the present invention, for example, when the ink is ejected by the ink jet head of the ink jet recording apparatus, corrosion of the ink jet head can be suppressed.

  In the discharging agent of the present invention, the blending amount of thiourea dioxide is not particularly limited, and is, for example, 0.5% by weight to 5% by weight, preferably 1% by weight to 5% by weight with respect to the total amount of the discharging agent. %, More preferably 2 wt% to 5 wt%.

  The monocarboxylate is not particularly limited, and is, for example, at least one of a formate, an aliphatic carboxylate, and an aliphatic carboxylic acid derivative salt. Examples of the formate include sodium formate and potassium formate. Examples of the aliphatic carboxylate include sodium acetate, potassium acetate, sodium butyrate, potassium butyrate and the like. Examples of the aliphatic carboxylic acid derivative salt include sodium chloroacetate, potassium chloroacetate, sodium glycolate, potassium glycolate, sodium pivalate (sodium trimethylate), potassium pivalate (potassium trimethylate), and the like.

  Examples of the ascorbate include sodium ascorbate and potassium ascorbate. The ascorbic acid includes L-form and D-form, and any salt may be used, or a mixture of both salts may be used.

  Examples of the metasilicate include sodium metasilicate and potassium metasilicate.

  Said (i) may be used individually by 1 type, and may use 2 or more types together. In the discharging agent, the blending amount of (i) is not particularly limited, and is, for example, 0.5% by weight to 10% by weight, preferably 2% by weight to 10% by weight with respect to the total amount of the discharging agent. More preferably, it is 2 to 5% by weight.

  In the “β-diketone”, the “ketone” includes all of carbonyl compounds (aldehyde, carboxylic acid, ester, etc.) and salts, ions and hydrates thereof. The β-diketone is not particularly limited. For example, acetylacetone, sodium malonate (monosodium malonate, disodium malonate), potassium malonate (monopotassium malonate, dipotassium malonate), 3-acetyl-γ -Butyl lactone, dehydroacetic acid, methyl acetoacetate and the like are mentioned, and acetylacetone, disodium malonate, 3-acetyl-γ-butyllactone, dehydroacetic acid, methyl acetoacetate and N-methylacetoacetamide are preferred.

  The β-diketone may be used alone or in combination of two or more. In the discharging agent, the blending amount of the β-diketone is not particularly limited, and is, for example, 1% by weight to 15% by weight, preferably 2% by weight to 15% by weight with respect to the total amount of the discharging agent. .

The discharging agent of the present invention may further contain acetone or an acetone derivative. Examples of the acetone derivative include compounds represented by the following chemical formula. In the chemical formula, R ₁ and R ₂ are an alkyl group or hydrogen. The alkyl group is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms. The alkyl group may be, for example, linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group, a pentyl group, a hexyl group, and a heptyl group. Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like. Examples of the compound represented by the following chemical formula include 2-hydroxy-2-methyl-4-pentanone. The blending amount of the acetone or the acetone derivative is not particularly limited, and is, for example, 1% by weight to 10% by weight, and preferably 2% by weight to 10% by weight with respect to the total amount of the discharging agent.

  The discharging agent of the present invention may further contain (iii) an amine base. Examples of the amine base include primary amines, which may have one amino group or a plurality of amine groups. Examples of the primary amine include amino alcohols, guanidine salts or guanidine derivatives, N, N′-bis (2-aminoethyl) -1,2-ethanediamine, and the like. Specific examples of the amino alcohol include, for example, 2-amino-2-hydroxymethyl-1,3-propanediol (AHP), 2-amino-2-methyl-1-propanol (AMP), and 2-amino-2. -Ethyl-1,3-propanediol (AEP), 2- (2-aminoethoxy) ethanol (AEE) and the like. Examples of the guanidine salt include guanidine carbonate, and examples of the guanidine derivative include aminoguanidine sulfate. The blending amount of the (iii) amine base is not particularly limited, and is, for example, 1% by weight to 10% by weight, and preferably 2% by weight to 10% by weight with respect to the total amount of the discharging agent. By including the amine base in the discharging agent, the discharging agent of the present invention can be stabilized over a long period of time, for example, one month after preparation (28 days later).

  The discharging agent of the present invention may further contain water. The water is, for example, ion exchange water or pure water. The blending amount of the water with respect to the total amount of the discharging agent may be, for example, the remainder of the other components.

  The discharging agent of the present invention may further contain a water-soluble organic solvent. A conventionally well-known thing can be used as said water-soluble organic solvent. Examples of the water-soluble organic solvent include polyhydric alcohol, polyhydric alcohol derivative, alcohol, amide, keto alcohol, ether, nitrogen-containing solvent, sulfur-containing solvent, propylene carbonate, ethylene carbonate, 1,3-dimethyl-2- Examples include imidazolidinone. Examples of the polyhydric alcohol include glycerin (Gly), ethylene glycol, diethylene glycol (DEG), propylene glycol, butylene glycol, hexylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, Examples thereof include trimethylolpropane, 1,5-pentanediol, 1,2,6-hexanetriol and the like. Examples of the polyhydric alcohol derivative include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol-n-propyl ether, Diethylene glycol-n-butyl ether, diethylene glycol-n-hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol-n-propyl ether, triethylene glycol-n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl Ether, propylene glycol-n-propyl Ether, propylene glycol-n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol-n-propyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, Examples include tripropylene glycol-n-propyl ether and tripropylene glycol-n-butyl ether. Examples of the alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, and benzyl alcohol. Examples of the amide include dimethylformamide and dimethylacetamide. Examples of the keto alcohol include diacetone alcohol. Examples of the ether include tetrahydrofuran and dioxane. Examples of the nitrogen-containing solvent include pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, triethanolamine, and the like. Examples of the sulfur-containing solvent include thiodiethanol, thiodiglycol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like. The blending amount of the water-soluble organic solvent with respect to the total amount of the discharging agent is, for example, 0.5 wt% to 30 wt%, preferably 5 wt% to 30 wt%, more preferably 10 wt% to 20% by weight. The water-soluble organic solvent may be used alone or in combination of two or more.

  The water-soluble organic solvent is, for example, at least one of Gly and DEG, which are high-boiling solvents, and is, for example, Gly. The blending amount of the high boiling point solvent with respect to the total amount of the discharge agent is, for example, 0.5 wt% to 30 wt%, for example, 5 wt% to 30 wt%, preferably 10 wt% to 20 wt%. It is.

  The discharging agent of the present invention may further contain a conventionally known additive as required. Examples of the additive include a surfactant, a viscosity modifier, a surface tension modifier, an antioxidant, and an antifungal agent. Examples of the viscosity modifier include polyvinyl alcohol, cellulose, and a water-soluble resin.

  In the discharge agent of the present invention, for example, components other than thiourea dioxide and at least one of the above (i) and (ii) are mixed in advance, and thiourea dioxide and the components (i) and (ii) are mixed therein. It can be prepared by adding at least one.

  Next, the storage container of the present invention will be described. The storage container includes the discharge agent of the present invention. As the main body of the container, for example, a conventionally known one such as one similar to the ink tank 20 in the ink jet printer 1 shown in FIG. For example, an ink cartridge having a resin casing or an ink pack formed of a flexible film can be used as the main body of the container. If an impact occurs when the discharge agent is placed in a flexible ink pack, if a chemical reaction proceeds and there is a concern about deterioration of the discharge function, a storage container having a housing should be used. it can. In this case, the discharging agent may be put directly into the housing. Further, the discharging agent may be placed in a flexible ink pack disposed inside the casing. Furthermore, the discharging agent may be put in a gap between an ink pack made of a flexible material and a housing wall. In addition, only the solid of the discharging agent may be put in the container and mixed with the liquid later.

  Next, the ink jet recording apparatus of the present invention will be described. The ink jet recording apparatus is an ink jet recording apparatus having a liquid discharge means for discharging a liquid, and further includes means for applying the discharging agent of the present invention. Examples of the liquid include ink for ink jet recording, a treatment liquid used for ink jet recording, and the like. The ink jet recording apparatus may further include a storage unit that stores a storage container, and the liquid discharge unit discharges the liquid inside the storage container stored in the storage unit. As an apparatus having such a configuration, for example, a configuration in which means for applying the discharging agent is added to the ink jet recording apparatus shown in FIG. Examples of the means for applying the discharging agent include an ink jet head, a spray, a stamp for applying the discharging agent to the fabric, a brush, a roller, and the like. In the present embodiment, the inkjet head 5 shown in FIG. 3 is provided as means for applying (discharging) the discharging agent. The ink jet recording apparatus may further include a discharge agent storage portion that stores the discharge agent.

  Next, the discharging method of the present invention will be described. The discharging method is a fabric discharging method, and includes a discharging agent applying step of applying the discharging agent to the fabric, and a heating step of heating an application portion of the discharging agent.

  In the discharge agent application step, the discharge agent can be applied by, for example, an ink jet method using an ink jet head (spray method), a spray method, a stamp application, a brush application, a roller application, or the like. In the discharging method, since the discharging agent using thiourea dioxide and at least one of the above (i) and (ii) is used, when the discharging agent is applied (discharged) by an inkjet method, Corrosion can be suppressed.

  In the discharging agent application step, the discharging agent may be applied to the entire image forming surface of the fabric or a part thereof. In the case of applying to a part, at least an area on the image forming surface of the fabric that is substantially the same as the printed part with ink becomes the application part. When applying to a part, the size of the application part is preferably larger than the printed part. For example, as shown in FIG. 1A, when printing a character (X) on a fabric (T-shirt in this example) 100, the application unit 110 is formed with a line width larger than the line width of the character. A discharge agent is applied to form. Further, for example, as shown in FIG. 1B, when printing a design on a fabric (T-shirt) 100, for example, a discharging agent is applied so as to form an application part 120 larger than the design. .

  Next, the said heating process is a process of heating the application part of the said discharge agent. The said heating can be implemented using commercially available iron, a hot press machine, oven, a belt conveyor oven, etc., for example. When using an iron or a hot press machine, for example, heating is performed in a state where a Teflon (registered trademark) sheet having a smooth surface is placed on the application part of the discharging agent. As a result, it is possible to suppress the fabric from being scraped. For example, when the discharging method is used in an image forming method described later, printing of an image can be performed more smoothly. Although the said heating temperature is not restrict | limited in particular, For example, it is the range of 160 to 185 degreeC. In the discharge method, since the discharge agent using thiourea dioxide and at least one of the above (i) and (ii) is used, the discharge agent that has been used for about one month is used after long-term storage. In this case, the fabric can be discharged and formaldehyde is not generated.

  Next, the image forming method of the present invention will be described. The image forming method is an image forming method for forming an image on a fabric, and includes a discharging process for discharging the fabric, and an image printing process for printing an image using ink at the discharged portion. The step is performed by the discharging method of the present invention.

  For example, the image forming method may include a process such as a thermal fixing process described later in addition to the two processes.

  The discharging process is as described in the discharging method.

  Next, the image printing step is a step of printing an image using ink on the discharged portion or the portion where the discharging agent is applied. In addition, when printing an image using the ink in the location which applied the said discharging agent, after heating an image using an ink, you may perform the heating process in the above-mentioned discharging method. The ink used in the image printing process is not particularly limited. For example, pigment ink, dye ink, and the like can be used, and pigment ink is used.

  The image printing step can be performed using, for example, an ink jet recording apparatus shown in FIG. In the ink jet recording apparatus of this example, the image printing process is performed by an ink jet method. As shown in the figure, the inkjet recording apparatus includes an inkjet printer 1 that prints a desired image by ejecting ink onto a fabric, and a print control apparatus 70 that acquires image data of the desired image and controls the inkjet printer 1. Are connected via an interface.

  As shown in FIG. 3, the ink jet printer 1 includes a frame-like frame 2. The frame 2 has a horizontal portion 2h located at the bottom of the printer 1 and two vertical portions 2v that rise vertically from both ends of the horizontal portion 2h. 3, the same parts as those in FIG. 2 are denoted by the same reference numerals, and the same applies to the drawings subsequent to FIG.

  The slide rail 3 is horizontally supported so as to connect the upper portions of the two vertical portions 2v. The slide rail 3 is provided with a carriage 4 slidably along the longitudinal direction (main scanning direction) of the slide rail 3. On the lower surface of the carriage 4, five piezoelectric inkjet heads (liquid ejection means) 5 are provided for each color in order to eject five colors of ink. For example, the inkjet printer 1 may have a configuration in which eight inkjet heads are provided. Specifically, four inkjet heads arranged in the carriage movement direction are used as one head unit, and the two head units are arranged to face each other in a direction orthogonal to the carriage movement direction. Also good. In this case, one head unit is provided with four inkjet heads that respectively discharge four color inks (cyan, magenta, yellow, and black), and the other head unit discharges white ink. Two inkjet heads and two inkjet heads for discharging the discharging agent are provided.

  Pulleys 6 and 7 are supported on the upper portions of the two vertical portions 2v, respectively, and a motor shaft of a motor 8 supported by the vertical portions 2v is connected to one pulley 6. An endless belt 9 is stretched between the pulleys 6 and 7, and the carriage 4 is fixed to an appropriate portion of the endless belt 9.

  With such a configuration, when one pulley 6 is rotated forward and backward by driving the motor 8, the carriage 4 is linearly reciprocated along the longitudinal direction (main scanning direction) of the slide rail 3 accordingly. As a result, the inkjet head 5 is reciprocated.

  The two vertical portions 2v are each provided with a mounting portion 10 on which the ink tank 20 is detachably mounted. The two mounting portions 10 are configured such that one of two colors and the other three colors of ink tanks 20 can be mounted. An ink bag (not shown) formed inside the ink tank 20 is provided. The flexible tubes 28 are connected to the five sub tanks 30 located on the respective upper portions of the inkjet head 5. Since the five sub tanks 30 communicate with the inkjet head 5 as will be described later, ink is supplied from the ink tank 20 to the inkjet head 5.

  A slide mechanism 11 is installed on the horizontal portion 2 h of the frame 2, and a platen (support) 12 is supported on the slide mechanism 11. The platen 12 is provided with a fixing frame (fixing means) 15 so that the fabric can be positioned so that the printed portion is on the upper surface and can be set in a flat state without a tight wrinkle. . In addition, although the inkjet printer 1 of this example performs inkjet recording on a sewn T-shirt, it can be applied to all fabrics. In the inkjet printer 1 of this example, the number of the platens 12 is one. However, the number of platens is not limited to one and can be increased as necessary. For example, if an inkjet printer having two platens is used, the T-shirt can be fixed to the other platen while an image is printed on the T-shirt fixed to one platen, and the work efficiency can be improved. Can be increased.

  Further, a platen transport mechanism is provided to reciprocate the platen 12 in the direction perpendicular to the plane of FIG. 3 (the slide direction in the slide mechanism 11 and the sub-scanning direction of the inkjet printer 1) (FIG. Not shown). As the platen transport mechanism, for example, a rack, a pinion mechanism, a mechanism using an endless belt, or the like can be applied.

  FIG. 4 shows a state in which the fabric is set on the platen. 4A is a plan view, and FIG. 4B is a cross-sectional view as seen from the AA direction in FIG. 4A. As shown in the figure, the platen 12 has a rectangular shape having a longitudinal direction in a direction orthogonal to the reciprocating direction of the carriage 4 in plan view, and has a support surface 16 that supports the T-shirt 100. . Further, the lower surface of the platen 12 on the back side in the direction perpendicular to the paper surface of FIG. 4B is connected by a slide mechanism 11 and a support member 17 at a position facing it. Further, the upper ends of both ends parallel to the longitudinal direction of the platen 12 are formed in an arc shape.

  The fixed frame 15 is configured such that a frame having an L-shaped cross section covers four sides of the support surface 16 of the platen 12. An opening 15 a having an opening area slightly smaller than the area of the support surface 16 of the platen 12 is formed on the surface of the fixed frame 15 facing the support surface 16 of the platen 12. A rubber anti-slip member 19 is provided on the inner surface of the fixed frame 15 facing the side surface of the platen 12. By providing the anti-slip member 19, when the T-shirt 100 is set on the platen 12, the longitudinal direction (vertical direction of the T-shirt 100) and the short direction of the support surface 16 of the platen 12. It is possible to set the T-shirt 100 in a stretched state in two directions (lateral direction of the T-shirt 100), and the T-shirt 100 can be held without wrinkles. When the T-shirt 100 is set on the platen 12, the T-shirt 100 is covered with the support surface 16 of the platen 12 from the hem side of the T-shirt 100 and fixed by the fixed frame 15. Further, the fixed frame 15 is rotatably provided by a rotating portion (not shown) provided at an end portion of the platen 12 on the back side in the direction perpendicular to the paper surface of FIG. After the shirt 100 is put on the platen 12, the fixed frame 15 is rotated so as to fit the platen 12, and the T-shirt 100 is fixed by being sandwiched between the platen 12 and the fixed frame 15. .

  The ink jet printer 1 includes a cover 13 so as to cover and protect the ink jet head 5 and the slide mechanism 11. In FIG. 3, in order to show the inside of the cover 13 in detail, the cover 13 is depicted in a perspective manner by a two-dot chain line. An operation panel 14 having a liquid crystal panel and operation buttons is disposed on the upper right portion of the front surface of the cover 13.

  The five inkjet heads 5 shown in FIG. 3 correspond to five colors of ink (white, yellow, magenta, cyan, black) and are arranged in parallel along the reciprocating direction of the carriage 4. The ink tank 20 communicates with the flexible tube 28 and the sub tank 30. As a configuration for supplying ink to the ink jet head, for example, a conventionally known one can be used (see, for example, JP-A-2004-291461).

  In this way, by connecting the ink tank 20 and the sub tank 30 with the flexible tube 28, the ink in the ink tank 20 can be supplied to the sub tank 30, and the ink tank 20 It can be provided at a position where replacement is easy. Therefore, the ink tank 20 can be easily replaced when the ink in the ink tank 20 runs out.

  The inkjet head 5 is arranged such that its lower surface forms a slight gap with the support surface 16 of the platen 12, and is set on the platen 12 when printing an image on the T-shirt 100. The printed portion of the T-shirt 100 is conveyed into the gap. With this configuration, the ink-jet head 5 is reciprocated by the carriage 4 to eject ink of each color from a small-diameter discharge nozzle formed on the bottom surface of the ink-jet head 5 on the T-shirt 100. A desired color image can be printed on the T-shirt 100.

  2 is configured using, for example, a general-purpose personal computer (PC), and includes a main body 71, a display as a display unit 72, a keyboard 73 and a mouse (pointing device) as an operation unit 75. 74.

  FIG. 5 is a block diagram showing the configuration of the print control apparatus 70 shown in FIG. The print control device 70 includes a CPU (Central Processing Unit) 81, a ROM (Read Only Memory) 82, a RAM (Random Access Memory) 83, an HD (Hard Disk) 84, an operation unit 75, a display unit 72, an interface (I / I). F) 85, which are connected to each other via a bus. The CPU 81, the ROM 82, the RAM 83, and the HD 84 are incorporated in the main body 71 of the print control apparatus 70, and the operation unit 75 includes the keyboard 73 and the mouse 74.

  The HD 84 stores various programs used for controlling the operation of the print control apparatus 70. The HD 84 stores various image data created by software and various data for each type of fabric such as a T-shirt. The CPU 81 performs various calculations and processing based on signals input from the operation unit 75 and various programs and data in the ROM 82, the RAM 83, and the HD 84. Then, data or the like is transmitted to the inkjet printer 1 via the interface 85. The RAM 83 is a readable / writable volatile storage device, and stores various calculation results in the CPU 81. The interface 85 is connected to the interface of the ink jet printer 1 and enables communication between the print control device 70 and the ink jet printer 1.

  FIG. 6 is a functional block diagram of the print control apparatus 70. As illustrated, the print control apparatus 70 includes an image data acquisition unit 90 and an image data storage unit 91. In this example, the image data acquisition unit 90 is realized by the CPU 81, and the image data storage unit 91 is configured by the RAM 83 or the HD 84.

  The image data acquisition unit 90 has a known function for creating image data, and creates various image data based on signals input by the operator through the keyboard 73 and the mouse 74. The image data storage unit 91 stores image data collected from a removable storage medium such as a CD-ROM, FD, or MO, the Internet, or the image data acquired by the image data acquisition unit 90.

  Printing of a desired image on the T-shirt 100 using the inkjet recording apparatus of this example can be performed as follows, for example. First, image data to be printed on the T-shirt 100 is acquired through the keyboard 73 and the mouse 74 of the PC. In obtaining the image data, image data is created using software installed in the PC, or image data stored in advance in the HD 84 is selected.

  Next, the T-shirt 100 is fixed to the platen 12. That is, the T-shirt 100 is put on the platen 12 from the hem, and is fixed by the fixed frame 15 along the support surface 16 of the platen 12 without any wrinkles.

  Next, when an operator instructs the execution of printing, the image data is transmitted to the inkjet printer 1 via the interface 85, and ink is ejected from the inkjet head 5 based on the image data. Printing on the fixed T-shirt 100 is performed.

  The ink jet recording apparatus may further include a heating unit. The heating means may be any means as long as the heat fixing process described later can be performed in the ink jet recording apparatus. The heating means is means that can apply pressure to the printing portion of the fabric such as hot press means together with heating. In addition to the heating means, a pressurizing means may be provided. Either the heating or the pressurization may be performed first, or both may be performed simultaneously. Further, as will be described later, the heat fixing step may be performed by an apparatus having a heating means and a pressure means different from the ink jet recording apparatus.

  The ink jet recording apparatus may not include the ink tank for white ink and the ink jet head. In the image forming method, since an image is printed on the fabric after discharging, a color image can be formed on a fabric of dark color without forming a base layer with white ink.

  In this example, the image printing step is performed by an ink jet method, but the image printing step may be performed by screen printing, gravure printing, stencil, or the like using a conventionally known apparatus or means.

  Next, the image forming method may include a heat fixing step of heat-fixing the ink on the fabric by performing a heat treatment on the printed portion of the fabric after the image printing step. The heat fixing step can be performed with the same apparatus and conditions as the heating step of the discharging method. The heat fixing step can also be performed using, for example, an apparatus described in Japanese Patent Application Laid-Open No. 2009-209493. According to this apparatus, it is possible to apply pressure to the fabric together with heating at 180 ° C.

Next, the stabilizer for the discharge agent of the present invention will be described. The discharging agent stabilizer is a discharging agent stabilizer containing thiourea dioxide, and the discharging agent contains at least one of the following (i) and (ii). In the discharge agent stabilizer, the conditions such as the type and blending amount of at least one of (i) and (ii) may be the same as those of the above-described discharge agent.

(I) at least one salt selected from the group consisting of monocarboxylate, ascorbate and metasilicate (ii) β-diketone

Next, a method for stabilizing the discharging agent of the present invention will be described. The method for stabilizing the discharging agent is a method for stabilizing a discharging agent containing thiourea dioxide, wherein at least one of the following (i) and (ii) is added to the discharging agent. In the method for stabilizing the discharge agent, the conditions such as the type and blending amount of at least one of (i) and (ii) may be the same as those for the above-described discharge agent.

(I) at least one salt selected from the group consisting of monocarboxylate, ascorbate and metasilicate (ii) β-diketone

  Next, examples will be described together with comparative examples. In addition, this invention is not limited and restrict | limited by the following Example and comparative example.

[Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-10]
Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-10 are examples of discharging agents containing thiourea dioxide and the above (i). In the discharging agent composition (Table 1 or Table 2), components other than thiourea dioxide and salt were mixed, and thiourea dioxide and salt were added thereto, so that Examples 1-1 to 1-17 and Comparative Example 1 were added. -1 to 1-10 discharging agents were obtained.

  The storage stability of the discharging agents of Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-10 was evaluated by the following method. That is, first, a sheet obtained by cutting out the discharge agents of Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-10 immediately after preparation, 24 hours and 72 hours into 5 cm squares within 1 hour. It sprayed 7 times by the spray system to Oita T-shirt (Brand name made by Hanes: BEEFY (black)). Subsequently, the application part was heated while moving an iron in a state where a Teflon (registered trademark) sheet having a smooth surface was placed on the application part of the discharging agent. Next, the T-shirt was normally washed with a washing machine (with detergent) and then naturally dried in the shade. The degree of discharge of the T-shirt was evaluated according to the following evaluation criteria with reference to the discharge agent immediately after preparation without adding salt.

Evaluation of Storage Stability of Discharge Agent Evaluation AA: Color was significantly missing from the reference A: Color was missing from the reference B: Color was missing from the reference, but discoloration was observed C: Color Omission was equal to or less than the reference

  Table 1 shows the compositions and evaluation results of the discharging agents of Examples 1-1 to 1-17. In addition, Table 2 shows the compositions and evaluation results of the discharging agents of Comparative Examples 1-1 to 1-10.

  As shown in Table 1, in Examples 1-1 to 1-17, even after 72 hours from the preparation of the discharge agent, the color was missing from the reference. On the other hand, as shown in Table 2, in Comparative Example 1-1 in which the specific salt was not used, the color loss became equal to or less than that of the reference after 24 hours from the preparation of the discharge agent, and instead of the specific salt, an amino acid Even in Comparative Examples 1-2 to 1-10 using a compound other than the specific salt such as the above, the color loss became equal to or less than that of the reference immediately after the preparation of the discharge agent or after 72 hours. As described above, the discharge using thiourea dioxide increases the effective yield of sulfoxylic acid because the reaction intermediate is stabilized by the nucleophilic action of carbonyl carbon. As a result, it is presumed that the discharging effect has been improved.

[Examples 1-18 to 1-27]
Examples 1-18 to 1-27 are also examples of discharge agents containing thiourea dioxide and (i). In the discharge agent composition (Table 3), components other than thiourea dioxide and salt were mixed, and thiourea dioxide and salt were added thereto to obtain discharge agents of Examples 1-18 to 1-27.

  The storage stability of the discharging agents of Examples 1-18 to 1-27 was evaluated by the following method. That is, first, immediately after preparation, a T-shirt (manufactured by Hanes Co., Ltd.) having a sheet obtained by hollowing out the discharge agent of Examples 1-18 to 1-27 in Examples 1-18 to 1-27 after 5 days within 1 hour. (Product name: BEEFY (black)) was sprayed seven times by a spray method. Subsequently, the application part was heated while moving an iron in a state where a Teflon (registered trademark) sheet having a smooth surface was placed on the application part of the discharging agent. Next, the T-shirt was normally washed with a washing machine (with detergent) and then naturally dried in the shade. The degree of discharge of the T-shirt was evaluated by the optical density (OD value) measured using a spectrocolorimeter SpectroEye (light source: D65 / 10) manufactured by X-Rite. The lower the OD value, the more colors are missing. In addition, the OD value of the T-shirt before discharging was 1.7.

  Table 3 shows the compositions and evaluation results of the discharging agents of Examples 1-18 to 1-27.

  As shown in Table 3, in Examples 1-18 to 1-27 using Gly, which is a high boiling point solvent, the OD value decreased by 0.1 or more from 1.7 before discharge after 14 days from the preparation of the discharge agent. However, the color was missing so that the difference could be confirmed visually.

[Examples 2-1 to 2-7]
Examples 2-1 to 2-7 are examples of discharging agents containing thiourea dioxide and the above (ii).
In the discharge agent composition (Table 1), the components except for thiourea dioxide and β-diketone are mixed,
The discharging agent of Examples 2-1 to 2-7 was obtained by adding thiourea dioxide and β-diketone thereto.

  The storage stability of the discharging agents of Examples 2-1 to 2-7 was evaluated in the same manner as in Examples 1-18 to 1-27.

  Table 4 shows the compositions and evaluation results of the discharging agents of Examples 2-1 to 2-7.

  As shown in Table 4, in Examples 2-1 to 2-7, after 14 days from the preparation of the discharging agent, the OD value was significantly reduced from 1.7 before discharging, and the color was considerably lost. As described above, in the discharge using thiourea dioxide, the reaction intermediate is stabilized by the nucleophilic action of carbonyl carbon, and the intermediate is decomposed over time, so that the effective residence time of sulfoxylic acid is long. Become. As a result, it is presumed that the discharging effect has been improved.

[Examples 2-8 to 2-10 and Comparative Examples 2-1 to 2-2]
Examples 2-8 to 2-10 and Comparative Examples 2-1 to 2-2 are also examples of discharging agents containing thiourea dioxide and the above (ii). In the discharge agent composition (Table 5), components other than thiourea dioxide and β-diketone (2-hydroxy-2-methyl-4-pentanone in Comparative Example 2-2) were mixed, and thiourea dioxide and By adding β-diketone, discharge agents of Examples 2-8 to 2-10 and Comparative Examples 2-1 to 2-2 were obtained.

  Example 1-8 except that the storage stability of the discharging agents of Examples 2-8 to 2-10 and Comparative Examples 2-1 to 2-2 was changed after 2 days and the OD value was measured after 28 days. Evaluation was performed in the same manner as in 18 to 1-27.

  Table 5 shows the compositions and evaluation results of the discharging agents of Examples 2-8 to 2-10 and Comparative Examples 2-1 to 2-2.

  As shown in Table 5, in Examples 2-8 to 2-10, after 28 days from the preparation of the discharging agent, the OD value was significantly reduced from 1.7 before discharging, and the color was considerably lost. On the other hand, in Comparative Example 2-1 that did not use β-diketone and Comparative Example 2-2 that used 2-hydroxy-2-methyl-4-pentanone instead of β-diketone, 28 After a day, the OD value was close to 1.7 before discharging.

[Examples 3-1 to 3-3]
Examples 3-1 to 3-3 are examples of discharge agents containing thiourea dioxide and the above (i) and (ii). In the discharge agent composition (Table 6), the components except for thiourea dioxide, sodium formate and acetylacetone were mixed, and thiourea dioxide, sodium formate and acetylacetone were added thereto, whereby Examples 3-1 to 3-3 A discharge agent was obtained.

  The storage stability of the discharging agents of Examples 3-1 to 3-3 was evaluated in the same manner as in Examples 1-18 to 1-27.

  Table 6 shows the compositions and evaluation results of the discharge agents of Examples 3-1 to 3-3.

  As shown in Table 6, in Examples 3-1 to 3-3, after 14 days from the preparation of the discharging agent, the OD value was significantly reduced from 1.7 before discharging, and the color was considerably lost. As described above, in the discharge using thiourea dioxide, the reaction intermediate is stabilized by the nucleophilic action of the carbonyl carbon, and the intermediate is decomposed over time, so that the effective yield of sulfoxylic acid increases. , The residence time becomes longer. As a result, it is presumed that the discharging effect has been improved.

[Examples 4-1 to 4-3]
Examples 4-1 to 4-3 are examples of discharge agents containing thiourea dioxide, β-diketone (above (ii)), and amine base (above (iii)). Example 4-2 further includes a β-diketone, and Example 4-3 further includes a ketone. In the discharge agent composition (Table 7), thiourea dioxide, disodium malonate (above (i)), 2-amino-2-hydroxymethyl-1,3-propanedilol (AHP, amine base (above (iii))) ) Was completely dissolved in water. Thereafter, as shown in Table 7, N-methylacetoacetamide was added in Example 4-2, and 2-hydroxy-2-methyl-4-pentanone was added in Example 4-3. This obtained the discharging agent of Examples 4-1 to 4-3.

  The storage stability of the discharging agents of Examples 4-1 to 4-3 was evaluated by the following method. That is, first, a sheet obtained by punching out the discharge agent of Examples 4-1 to 4-3 in 5 cm square immediately after preparation, 0.5 months later, 1 month later, 2 months later, and 3 months later was placed. It sprayed 7 times by the spray method on the shirt (Brand name made from Hanes company: BEEFY (black)). Subsequently, the application part was heated while moving an iron in a state where a Teflon (registered trademark) sheet having a smooth surface was placed on the application part of the discharging agent. Next, the T-shirt was normally washed with a washing machine (with detergent) and then naturally dried in the shade. The degree of discharge of the T-shirt was evaluated by the optical density (OD value) measured using a spectrocolorimeter SpectroEye (light source: D65 / 10) manufactured by X-Rite. The lower the OD value, the more colors are missing. In addition, the OD value of the T-shirt before discharging was 1.7.

  Table 7 shows the compositions and evaluation results of the discharging agents of Examples 4-1 to 4-3.

  As shown in Table 7, in Examples 4-1 to 4-3, even after 2 months from the preparation of the discharging agent, the OD value was significantly reduced from 1.7 before discharging, and the color was considerably lost. . In particular, in Example 4-2 using N-methylacetoacetamide, which is a β-diketone, the OD value was the lowest, and even after 3 months from the preparation, an extremely low OD value was maintained. .

  As described above, the discharging agent of the present invention is capable of at least one of improving the discharging power and stabilizing the storage over a long period of time. The use of the discharging agent of the present invention is not particularly limited, and can be widely applied to discharging various fabrics.

1 Inkjet printer 4 Carriage 5 Inkjet head (liquid ejection means)
12 Platen (support)
DESCRIPTION OF SYMBOLS 15 Fixed frame 16 Support surface 70 Printing control apparatus 71 Main body 72 Display part 73 Keyboard 74 Mouse 90 Image data acquisition part 91 Image data storage part 100 T-shirt 110,120 Application | coating part

Claims (23)

A discharge agent containing thiourea dioxide,
Furthermore, the discharging agent characterized by including at least one of following (i) and (ii).

(I) at least one salt selected from the group consisting of monocarboxylate, ascorbate and metasilicate (ii) β-diketone
The discharging agent according to claim 1, wherein the monocarboxylate is at least one of a formate, an aliphatic carboxylate, and an aliphatic carboxylic acid derivative salt. 3. The discharging agent according to claim 2, wherein the aliphatic carboxylate is at least one of acetate and butyrate. The β-diketone is at least one selected from the group consisting of acetylacetone, disodium malonate, 3-acetyl-γ-butyrolactone, dehydroacetic acid, methyl acetoacetate, and N-methylacetoacetamide. The discharging agent according to any one of claims 1 to 3. The discharging agent according to any one of claims 1 to 4, comprising both (i) and (ii). Including at least one of (i) and (ii),
Furthermore, the discharging agent as described in any one of Claim 1 to 4 characterized by including the following (iii).

(Iii) amine base
The discharging agent according to claim 6, wherein (iii) is a primary amine base. The discharging agent according to claim 7, wherein (iii) is 2-amino-2-hydroxymethyl-1,3-propanediol (AHP). The blending amount of the thiourea dioxide is 0.5% by weight to 5% by weight with respect to the total amount of the discharge agent,
Furthermore, the compounding quantity of at least one of said (i) and (ii) is 1 weight%-15 weight% with respect to the said discharge agent whole quantity, It is any one of Claim 1 to 8 characterized by the above-mentioned. The discharge agent as described. A container containing a discharging agent, wherein the discharging agent is the discharging agent according to any one of claims 1 to 9. The storage container according to claim 10, wherein the main body of the storage container has a housing. An ink jet recording apparatus having a liquid discharging means for discharging a liquid,
And further includes means for applying a discharging agent,
An ink jet recording apparatus, wherein the discharging agent is the discharging agent according to any one of claims 1 to 9. A method for discharging fabric,
A discharging agent application step of applying a discharging agent to the fabric;
A heating step of heating the application part of the discharging agent,
The discharging method using the discharging agent as described in any one of Claim 1 to 9 as said discharging agent. An image forming method for forming an image on a fabric,
A discharging process for discharging the fabric;
An image printing step of printing an image using ink at the discharged spot,
An image forming method, wherein the discharging process is performed by the discharging method according to claim 13. The image forming method according to claim 14, wherein the image printing step is performed by an inkjet method. A stabilizer for a discharge agent containing thiourea dioxide,
The stabilizer characterized by including at least one of following (i) and (ii).

(I) at least one salt selected from the group consisting of monocarboxylate, ascorbate and metasilicate (ii) β-diketone
A stabilizer for a discharge agent containing thiourea dioxide,
The stabilizer according to claim 16, comprising both (i) and (ii). A stabilizer for a discharge agent containing thiourea dioxide,
Including at least one of (i) and (ii),
The stabilizer according to claim 16, further comprising (iii):

(Iii) amine base
The stabilizer according to claim 18, wherein (iii) is 2-amino-2-hydroxymethyl-1,3-propanediol (AHP).
A method for stabilizing a discharge agent containing thiourea dioxide,
A stabilization method comprising adding at least one of the following (i) and (ii):

(I) at least one salt selected from the group consisting of monocarboxylate, ascorbate and metasilicate (ii) β-diketone
21. The stabilization method according to claim 20, wherein both (i) and (ii) are added to the discharging agent. Including at least one of (i) and (ii),
Furthermore, the following (iii) is added, The stabilization method of Claim 20 characterized by the above-mentioned.

(Iii) amine base
The stabilization method according to claim 22, wherein (iii) is 2-amino-2-hydroxymethyl-1,3-propanediol (AHP).

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