JP6794650B2 - Printing method - Google Patents

Description

The present invention relates to a printing method.

The inkjet recording method is a method in which small droplets of ink are ejected from a fine nozzle and adhered to a recording medium for recording. This method is characterized in that high-resolution and high-quality images can be recorded at high speed with a relatively inexpensive device. In the inkjet recording method, there are numerous factors to be examined, such as the properties of the ink used, the stability in recording, and the quality of the obtained image, and research on not only the inkjet recording device but also the ink composition to be used is active. is there.

In addition, dyeing (printing) of fabrics and the like is also performed using an inkjet recording method. Conventionally, screen printing, roller printing, etc. have been used as printing methods for fabrics (woven fabrics and non-woven fabrics), but from the viewpoint of high-mix low-volume productivity and immediate printability, the inkjet recording method should be applied. Is advantageous, so various studies have been conducted.

When the ink composition is used for printing, the ink composition contains at least one coloring material of a dye and a pigment. When the coloring material is a dye, the dye is dyed relatively strongly on the fabric by chemical bonding or the like, but when the coloring material is a pigment, the pigment is physically fixed to the fibers of the fabric or the like. Is important.

Patent Document 1 discloses an attempt to improve the washing / rubbing fastness of a printed surface by applying a pigment printing ink, then performing a middle coat and an overcoat, and formulating the middle coat agent and the overcoat agent. ing. Further, in the technique described in Patent Document 2, a clear liquid having good wettability to the fabric is used to suppress the formation of ink lumps of the printing ink due to the fluffing of the fabric so that the coloring material reaches the surface of the fabric. So, I am trying to print with high image quality.

JP-A-2010-150454 Japanese Unexamined Patent Publication No. 2012-193472

Since the ink layer and the overcoat layer are formed in layers, the expansion and contraction of the overcoat layer cannot follow the expansion and contraction of the ink layer, causing peeling. Therefore, in the technique disclosed in Patent Document 1, an attempt is made to prevent the overcoat layer from peeling off by providing a layer called a middle coat layer between the overcoat layer and the ink layer. Further, Patent Document 1 describes that the peeling prevention effect cannot be obtained only by providing one layer in which the middle coating agent and the overcoating agent are mixed. Further, in the technique, the middle coat layer is formed after the ink layer is dried, and a strong ink film is formed.

However, in the method of drying the ink layer and then adhering the coat layer, adhesion between the coat layer and the ink layer may not be obtained, and it takes time to dry the ink layer. Therefore, in the printing step. It was difficult to save time.

On the other hand, in the technique described in Patent Document 2, the wettability of the clear liquid is improved, and a resin is added to the clear liquid to improve the fixability. However, since the clear liquid is applied by the inkjet method, there is a limit to increasing the amount of resin that can be added to the clear liquid in order to maintain the ejection stability.

One of the objects according to some aspects of the present invention is to provide a printing method capable of efficiently producing a printed product having excellent friction fastness and washing fastness.

The present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as the following aspects or application examples.

One aspect of the printing method according to the present invention is
A step of adhering an ink composition containing a pigment to a fabric by an inkjet method,
A step of adhering a treatment liquid containing the first resin to the cloth in a state where the drying rate of the ink composition is less than 90%.
including.

According to such a printing method, the pigment in the ink composition can be fixed to the fabric by the first resin in the treatment liquid, and a printed product having excellent friction fastness and washing fastness can be produced. .. Further, since the treatment liquid is adhered to the fabric in a state where the drying rate is low after the ink composition is adhered to the fabric, the ink composition and the treatment liquid are appropriately mixed, so that the fixability is good and the printed material is printed. The time required for production can be shortened, and a printed material having excellent friction fastness and washing fastness can be efficiently manufactured.

In the printing method according to the present invention
The first resin may be at least one selected from urethane-based, styrene-acrylic-based, acrylic-based, and vinyl chloride-vinyl acetate-based.

According to such a printing method, it is possible to further produce a printed product having excellent friction fastness and washing fastness.

In the printing method according to the present invention
The ink composition may contain a second resin.

According to such a printing method, it is possible to further produce a printed product having excellent friction fastness and washing fastness. Further, since the first resin is supplied by the treatment liquid, the blending amount of the second resin can be kept small, and the ink composition can easily have a viscosity suitable for the inkjet method.

In the printing method according to the present invention
The glass transition temperature of at least one of the first resin and the second resin may be 0 ° C. or lower.

According to such a printing method, since a resin having a lower elastic modulus is used, the ruggedness of the printed material (fabric) is suppressed, and a printed material having a better texture can be produced.

In the printing method according to the present invention
The first resin and the second resin may be similar resins.

According to such a printing method, the compatibility between the first resin and the second resin is improved, so that the blending amount of the entire resin can be suppressed and the fixability of the pigment can be further improved.

In the printing method according to the present invention
The step of adhering the treatment liquid may be performed by a method other than the inkjet method.

In this way, the first resin can be blended in a high concentration with respect to the treatment liquid. As a result, it is possible to produce a printed material having excellent friction fastness and washing fastness. Further, since the first resin is supplied from the treatment liquid, it is possible to prevent the second resin from being blended in the ink composition, or when the second resin is blended in the ink composition, the blending amount thereof. Can be kept small. Therefore, the compatibility of the ink composition with the inkjet method can be improved.

In the printing method according to the present invention
The step of adhering the treatment liquid may be started at a time of 1 second or more and 30 seconds or less after the step of adhering the ink composition.

In this way, when the treatment liquid containing the first resin is adhered to the fabric, it is easy to set the drying rate of the ink composition to less than 90%. Thereby, the fixability of the pigment can be further improved.

Some embodiments of the present invention will be described below. The embodiments described below describe an example of the present invention. The present invention is not limited to the following embodiments, and includes various modifications implemented without changing the gist of the present invention. It should be noted that not all of the configurations described below are essential configurations of the present invention.

The printing method according to the present embodiment includes a step of adhering the ink composition to the cloth and a step of adhering the treatment liquid to the cloth.

1. 1. Step of Adhering the Ink Composition to the Fabric The printing method of the present embodiment includes a step of adhering the ink composition to the fabric. This step is performed by an inkjet method. Hereinafter, the ink composition and the inkjet method will be described in this order.

1.1. Ink Composition The ink composition used in the printing method of the present embodiment contains at least a pigment.

1.1.1. Pigments The pigments are not particularly limited, and either inorganic pigments or organic pigments can be used. Examples of pigments include organic pigments such as azo-based, phthalocyanine-based, condensed polycyclic, nitro-based, nitroso-based, hollow resin particles, and polymer particles (Brilliant Carmine 6B, Lake Red C, Watching Red, Disazo Yellow, Hansa). Yellow, phthalocyanine blue, phthalocyanine green, alkaline blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, and nickel, titanium oxide, zinc oxide, antimony oxide, etc. Metal oxides and sulfides such as zinc sulfide and zirconium oxide, carbon blacks such as furnace carbon black, lamp black, acetylene black, and channel black (CI pigment black 7), as well as ocher, ultramarine, And inorganic pigments such as navy blue can be used.

The carbon black used as the black pigment is No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. (all manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven
1255, Raven 700, etc. (above, manufactured by Columbia Carbon Co., Ltd.), Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1100, Monarch 1100, Monarch 1100, Monarch 1100, Monarch 1 (The above is made by Cabot), Color
Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S160, Color Black S170, Print , Special Black 4A, Special Black 4 (all manufactured by Degussa) and the like.

As a white pigment, C.I. I. Pigment White 1 (basic lead carbonate), 4 (zinc oxide), 5 (mixture of zinc sulfide and barium sulfate), 6 (titanium oxide), 6: 1 (titanium oxide containing other metal oxides), 7 (Zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (titanium dioxide), 21 (barium sulfate), 22 (natural barium sulfate), 23 (gloss white), 24 (alumina white), 25 (plaster) ), 26 (magnesium oxide / silicon oxide), 27 (silica), 28 (anhydrous calcium silicate) and the like.

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

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

Examples of the cyan pigment include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, and C.I. I. Bat blue 4, 60 and the like can be mentioned.

Pigments other than black, white, yellow, magenta and cyan include, for example, C.I. I. Pigment Green 7, 10, and C.I. I. Pigment Brown 3, 5, 25, 26, and C.I. I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63 and the like.

A plurality of types of these illustrated pigments may be mixed and used. The total content of pigments (solid content) in the ink composition varies depending on the pigment type used, but is preferable when the total mass of the ink composition is 100% by mass from the viewpoint of obtaining good color development. Is 1 to 30% by mass, more preferably 2 to 15% by mass.

When preparing the ink composition, a pigment dispersion liquid in which the pigment is dispersed may be prepared in advance, and the pigment dispersion liquid may be added to the ink composition. Examples of the method for obtaining such a pigment dispersion include a method of dispersing a self-dispersing pigment in a dispersion medium without using a dispersant, a method of dispersing the pigment in a dispersion medium using a polymer dispersant, and a surface treatment. There is a method of dispersing the pigment in a dispersion medium.

1.1.2. Other components 1.1.2.1. Water The ink composition according to this embodiment may contain water. Examples of water include pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, and distilled water, and ultrapure water from which ionic impurities have been removed as much as possible. Further, when water sterilized by irradiation with ultraviolet rays or addition of hydrogen peroxide or the like is used, it is possible to prevent the outbreak of bacteria and fungi when the ink composition is stored for a long period of time.

The water content is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more, based on the total amount of the ink composition. The water in the ink composition includes, for example, a pigment dispersion liquid used as a raw material, a resin particle dispersion liquid, and water to be added. When the water content is 30% by mass or more, the ink composition can have a relatively low viscosity. The upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less with respect to the total amount of the ink composition. The term "water-based ink" as used herein refers to an ink containing 30% by mass or more of water with respect to the total mass (100% by mass) of the ink.

11.2.2. Water-soluble organic solvent The ink composition of the present embodiment may contain a water-soluble organic solvent. By containing the water-soluble organic solvent, it is possible to effectively suppress the evaporation of water from the recording head due to long-term standing while improving the ejection stability of the ink composition by the inkjet method.

Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, betaine compounds, pyrrolidone derivatives and the like.

Examples of the polyol compound include a polyol compound (preferably a diol compound) having 2 or more and 6 or less carbon atoms in the molecule and which may have one ether bond in the molecule. Specific examples include 1,2-pentanediol, methyl triglycol (triethylene glycol monomethyl ether), butyl triglycol (triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), and dipropylene glycol monopropyl ether. , Glycerin, 1,2-hexanediol, 1,2-heptanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butane Diol, 2-methyl-3-phenoxy-1,2-propanediol, 3- (3-methylphenoxy) -1,2-propanediol, 3-hexyloxy-1,2-propanediol, 2-hydroxymethyl- 2-Phenoxymethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,4-butanediol , 1,5-Pentanediol, 1,6-Hexanediol, 2-Methyl-2,4-Pentanediol, 3-Methyl-1,5-Pentanediol and other glycols.

Examples of the glycol ether include monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. preferable. More preferably, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monopropyl ether and the like can be mentioned.

A betaine compound is a compound that has positive and negative charges at non-adjacent positions in the same molecule, does not have a dissociable hydrogen atom bonded to an atom with a positive charge, and has no charge as a whole molecule. (Intramolecular salt). A preferred betaine compound is an N-alkyl substituent of an amino acid, more preferably an N-trialkyl substituent of an amino acid. Examples of betaine compounds include trimethylglycine (also referred to as "glycine betaine"), γ-butyrobetaine, homarin, trigonerin, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachidrine and betaine glutamate. Examples thereof are preferably made of trimethylglycine and the like.

A plurality of types of water-soluble organic solvents may be mixed and used. The total amount of the water-soluble organic solvent is 0.2% by mass or more and 30% by mass or less with respect to the total amount of the ink composition from the viewpoint of adjusting the viscosity of the ink composition and preventing clogging due to the moisturizing effect. It is preferably 0.4% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and further preferably 0.7% by mass or more and 10% by mass or less.

11.2.3. Surfactant The ink composition according to this embodiment may contain a surfactant. As the surfactant, any of nonionic surfactant, anionic surfactant, cationic surfactant, and amphoteric surfactant can be used, and these may be used in combination.

As the nonionic surfactant, at least one of an acetylene glycol-based surfactant, an acetylene alcohol-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant is preferable. When the ink composition contains these surfactants, the wettability to the fabric and the dispersion stability of the pigment are further improved.

The above-mentioned acetylene glycol-based surfactant and acetylene alcohol-based surfactant are not limited to the following, but are 2,4,7,9-tetramethyl-5-decine-4,7-diol and 2,4,7. , 9-Tetramethyl-5-decine-4,7-diol alkylene oxide adduct, and 2,4-dimethyl-5-decine-4-ol and 2,4-dimethyl-5-decine-4-ol, Selected from alkylene oxide adducts of 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexin-3ol, and 2,4-dimethyl-5-hexin-3-ol. Can exemplify more than one type. Commercially available products can also be used as the acetylene glycol-based surfactant and the acetylene alcohol-based surfactant, and surfinol 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 (all of the above are trade names, manufactured by AirProductsandChemicals. Inc.), Orfin 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, S
Examples thereof include K-14, AE-3 (all trade names above, manufactured by Nisshin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names above, manufactured by Kawaken Fine Chemical Co., Ltd.) and the like.

As the fluorine-based surfactant, a commercially available one may be used, and examples thereof include Megafuck F-479 (manufactured by DIC Corporation) and BYK-340 (manufactured by Big Chemie Japan Co., Ltd.).

As the polyorganosiloxane-based surfactant, commercially available ones can be used. For example, Orfin PD-501, Orfin PD-502, Orfin PD-570 (all manufactured by Nisshin Chemical Industry Co., Ltd.), BYK-347, BYK-348 (both manufactured by Big Chemie Co., Ltd.) and the like can be mentioned.

Further, examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyl glucoside, polyoxyalkylene glycol alkyl ether, polyoxyalkylene glycol, polyoxyalkylene glycol alkyl phenyl ether, and sucrose fatty acid. Esters, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene acetylene glycols, polyoxyalkylene glycol alkylamines, polyoxyethylene alkylamines, polyoxyethylene alkylamine oxides, fatty acid alkanolamides, archi Roll amide, polyoxyethylene polyoxypropylene block polymer and the like may be used.

Further, among the nonionic surfactants, the acetylene glycol-based surfactant is more preferably used because it has an excellent ability to maintain an appropriate surface tension and an interfacial tension and has a property of having almost no foaming property. be able to. That is, since the foaming property is small, it is difficult for bubbles to be trapped in the stepped portion of the ink flow path.

Examples of anionic surfactants include higher fatty acid salts, soaps, α-sulfo fatty acid methyl ester salts, linear alkylbenzene sulfonates, alkyl sulfate ester salts, alkyl ether sulfate ester salts, monoalkyl phosphate ester salts, and α. -Olefin sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, naphthalene sulfonate, alkane sulfonate, polyoxyethylene alkyl ether sulfate, sulfosuccinate, polyoxyalkylene glycol alkyl ether phosphate, etc. Can be mentioned.

Examples of the cationic surfactant include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt and an alkyldimethylbenzylammonium salt as a quaternary ammonium salt, and an N-methylbishydrochiethylamine fatty acid ester hydrochloride as an amine salt type.

Examples of the amphoteric surfactant include an alkylamino fatty acid salt as an amino acid type, an alkylcarboxylate betaine as a betaine type, and an alkylamine oxide as an amine oxide type. Amphoteric surfactants are not limited to these.

A plurality of types of the above-mentioned surfactant may be mixed and used. When the surfactant is blended in the ink composition, the total content of the surfactant is preferably 0.1 to 3% by mass when the total mass of the ink composition is 100% by mass.

11.2.4. Chelating agent The ink composition of the present embodiment may contain a chelating agent. The chelating agent has the property of capturing ions. Examples of such a chelating agent include ethylenediaminetetraacetate (EDTA), nitrilotriacetate of ethylenediamine, hexametaphosphate, pyrophosphate, and metaphosphate.

1.1.2.5. Preservatives The ink composition of this embodiment may contain preservatives. By containing the preservative, the growth of mold and bacteria can be suppressed, and the storage stability of the ink composition becomes better. This makes it easier to use, for example, the ink composition as a maintenance liquid for long-term maintenance without using a printer. Preferred examples of preservatives include Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel IB, Proxel TN and the like.

11.2.6. pH adjuster The ink composition of the present embodiment may contain a pH adjuster. By containing the pH adjuster, for example, the elution of impurities from the member forming the ink flow path can be suppressed or promoted, and the detergency of the ink composition can be adjusted. Examples of the pH adjuster include morpholins, piperazines, and amino alcohols such as triethanolamine.

11.2.7. Other Ingredients In the ink composition according to the present embodiment, various additives such as a viscosity modifier, a dissolution aid, an antioxidant, and an antifungal agent can be appropriately added.

11.2.8. Physical Properties of Ink Composition The ink composition according to this embodiment has a surface tension of 10 mN / m or more and 40 mN / m or less at 25 ° C. from the viewpoint of a balance between recording quality and reliability as an ink for inkjet recording. It is preferable, and it is more preferable that it is 25 mN / m or more and 40 mN / m or less. The surface tension is measured by checking the surface tension when the platinum plate is wet with ink in an environment of 25 ° C. using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.). be able to.

From the same viewpoint, the viscosity of the ink composition at 20 ° C. is preferably 2 mPa · s or more and 15 mPa · s or less, more preferably 2 mPa · s or more and 5 mPa · s or less, and 2 mPa · s or more. It is more preferably 3.6 mPa · s or less. The viscosity is measured by increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C. using a viscoelasticity tester MCR-300 (manufactured by Pysica) and reading the viscosity at Shear Rate 200. Can be measured.
1.2. Cloth The cloth to be printed by the printing method of the present embodiment is not particularly limited, and examples thereof include a cloth containing at least one of a hydrophobic fiber and a hydrophilic fiber. Further, in addition to the cloth, a sheet-like material such as a resin (plastic) film may be used. Examples of the fibers constituting the fabric include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended products using two or more of these fibers. Further, a blended product of these with recycled fibers such as rayon or natural fibers such as cotton, silk and wool may be used. Examples of the resin (plastic) film include polyester film, polyurethane film, polycarbonate film, polyphenylene sulfide film, polyimide film, polyamideimide film and the like. The resin (plastic) film may be a laminated body in which a plurality of layers are laminated, or may be composed of a functionally graded material whose composition of the material changes in a gradient manner.

1.3. Ink Composition Method The ink composition of the printing method of the present embodiment is adhered to the fabric by the inkjet method. The inkjet method is performed using, for example, the following inkjet recording device. The ink composition of the present embodiment can be suitably used for an inkjet recording device. The inkjet recording apparatus has at least an ink container (cartridge, tank, etc.) for accommodating the above-mentioned ink composition and a recording head connected to the container, and ejects the above-mentioned ink composition from the recording head to fabric (print). The image is not particularly limited as long as it can form an image.

As the inkjet recording device of this embodiment, either a serial type or a line type can be used. These types of inkjet recording devices are equipped with a recording head, and while changing the relative positional relationship between the fabric and the recording head, droplets of the ink composition are ejected from the nozzle hole of the recording head at a predetermined timing. (Intermittently) and with a predetermined volume (mass), the ink composition can be adhered to the cloth to form a predetermined image.

Here, in general, in a serial type inkjet recording device, the transport direction of the recording medium (fabric) and the reciprocating direction of the recording head intersect, and the reciprocating operation of the recording head and the transporting operation of the recording medium (reciprocating operation are also performed). Including), the relative positional relationship between the recording medium and the recording head is changed. Further, in this case, generally, a plurality of nozzle holes (holes for ejecting the ink composition) are arranged in the recording head, and a row of nozzle holes (nozzle row) is formed along the transport direction of the recording medium. There is. Further, the recording head may have a plurality of nozzle rows formed depending on the type and number of ink compositions.

Further, in general, in a line-type inkjet recording device, the recording head does not reciprocate, and the relative positional relationship between the recording medium and the recording head is changed by transporting the recording medium, so that the recording medium and the recording head are connected to each other. Change the relative positional relationship. Also in this case, in general, a plurality of nozzle holes are arranged in the recording head, and a row of nozzle holes (nozzle row) is formed along a direction intersecting the transport direction of the recording medium.

The inkjet recording method uses a serial type or line type inkjet recording device as described above, but as a method, the ink composition is ejected as droplets from a fine nozzle hole and the droplets are discharged as a recording medium. There is no particular limitation as long as it can be attached to. For example, examples of the inkjet recording method include an electrostatic suction method, a method of ejecting ink droplets by pump pressure, a method of using a piezoelectric element, a method of heating and foaming an ink liquid with a microelectrode, and ejecting ink droplets. it can.

For the inkjet recording device used in the present embodiment, for example, known configurations such as a heating unit, a drying unit, a roll unit, and a winding device can be adopted without limitation.

When the treatment liquid described later is adhered to the fabric by the inkjet recording device, for example, the ink composition and the treatment liquid are allocated to a plurality of nozzle rows at an appropriate ratio, and each nozzle is used. Therefore, the ink composition and the treatment liquid are adhered to the fabric.

2. 2. Step of Adhering the Treatment Liquid to the Fabric The printing method of the present embodiment includes a step of adhering the treatment liquid to the fabric. This step may be performed by a method other than the inkjet method, or may be performed by the inkjet method.

2.1. Treatment liquid The treatment liquid used in the printing method of the present embodiment contains at least the first resin.

2.1.1. First Resin The function of the first resin is to fix (fix) the pigment contained in the ink composition to the cloth. Further, when the ink composition contains the second resin, the first resin can improve the fixing of the pigment in cooperation with the second resin.

The first resin may be supplied in the form of a resin emulsion. When the first resin of the treatment liquid is blended in the form of an emulsion, the fixability of the pigment may be further improved, and the fastness of the image may be further improved.

Examples of such a first resin include, but are not limited to, at least one selected from urethane-based, styrene-acrylic-based, acrylic-based, and vinyl chloride-vinyl acetate-based. In the treatment liquid, one or more of these resins can be used. Among these, urethane-based resins are particularly preferable in terms of image fastness.

The urethane resin is not particularly limited as long as it has a urethane bond in the molecule, but in addition to the urethane bond, a polyether type urethane resin having an ether bond in the main chain and a polyester having an ester bond in the main chain. A type urethane resin, a polycarbonate type urethane resin containing a carbonate bond in the main chain, or the like can also be used.

As the first resin, a self-reactive urethane resin, a styrene acrylic resin, or an acrylic resin may be used. Examples of such self-reactive resins include urethane-based resins blocked with a blocking agent having a hydrophilic group, blocked urethane-based resins having a hydrophilic segment, carboxyl groups, hydroxyl groups, amino groups, methylol groups and the like. Examples thereof include an acrylic resin obtained by copolymerizing an acrylic monomer having a functional group.

The glass transition temperature (Tg) of the first resin is 5 ° C. or lower, preferably 0, from the viewpoint of suppressing the ruggedness of the printed material to improve the texture and improving the fastness of the image. ° C. or lower, more preferably −5 ° C. or lower, still more preferably −10 ° C. or lower, and particularly preferably −15 ° C. or lower. The lower limit of Tg is not particularly limited, but it is preferably −50 ° C. or higher from the viewpoint of improving the fastness of the image.

When the first resin is supplied as an emulsion, the D50 of the resin particles is preferably 30 nm or more and 300 nm or less, more preferably 40 nm or more and 100 nm or less. When D50 is within the above range, the resin emulsion particles can be uniformly dispersed in the treatment liquid. In addition, the scratch resistance of the printed matter is further improved.

As a commercial product of these resin emulsions,
Microgel E-1002, E-5002 (trade name manufactured by Nippon Paint Co., Ltd., styrene-acrylic resin emulsion),
Boncoat 4001 (DIC trade name, acrylic resin emulsion), Boncoat 5454 (DIC trade name, styrene-acrylic resin emulsion),
Polysol AM-710 (Tg: 56 ° C), AM-920 (Tg: -20 ° C), AM-2300 (Tg: 67 ° C), AP-4735 (Tg: 21 ° C), AT-860 (Tg: 60 ° C) ), PSASE-4210E (Tg: -50 ° C) (acrylic resin emulsion),
Polysol AP-7020 (Tg: 85 ° C) (styrene / acrylic resin emulsion), Polysol SH-502 (vinyl acetate resin emulsion, Tg: 30 ° C),
Polysol AD-13 (Tg: 18 ° C), AD-2 (Tg: 15 ° C), AD-10 (Tg: 8 ° C), AD-96 (Tg: -4 ° C), AD-17 (Tg: -10 ° C) ℃), AD-70 (
Tg: -25 ° C) (ethylene-vinyl acetate resin emulsion),
Polysol PSASE-6010 (Tg: -50 ° C) (ethylene-vinyl acetate resin emulsion) (trade name manufactured by Showa Denko KK),
Polysol SAE1014 (trade name, styrene-acrylic resin emulsion, manufactured by Zeon Corporation),
Cybinol SK-200 (trade name, acrylic resin emulsion, manufactured by Saiden Chemical Co., Ltd.),
AE-120A (trade name manufactured by JSR Corporation, acrylic resin emulsion, Tg: -10 ° C),
AE373D (trade name manufactured by E-Tech, carboxy-modified styrene / acrylic resin emulsion),
Seikadyne 1900W (trade name manufactured by Dainichiseika Kogyo Co., Ltd., ethylene-vinyl acetate resin emulsion),
Viniblanc 2682 (acrylic resin emulsion, Tg: -30 ° C),
Vinibran 2886 (vinyl acetate / acrylic resin emulsion, Tg: 0 ° C),
Vinibran 5202 (acrylic acetate resin emulsion, Tg: 30 ° C) (trade name manufactured by Nissin Chemical Industry Co., Ltd.),
Elitel KA-5071S (Tg: 67 ° C), KT-8803 (Tg: 61 ° C), KT-9204 (Tg: 19 ° C), KT-8701 (Tg: 13 ° C), KT-8904 (Tg: 10 ° C) , KT-0507 (Tg: -27 ° C) (Product name manufactured by Unitika Ltd., polyester resin emulsion),
Hi-Tech SN-2002 (trade name manufactured by Toho Chemical Industry Co., Ltd., polyester resin emulsion, Tg: 76 ° C),
Takelac W-6020 (Tg: 90 ° C), W-635 (Tg: 70 ° C), W-6061 (Tg: 25 ° C), W-605, W-635, WS-6021 (Tg: -60 ° C, 40) ℃) (trade name manufactured by Mitsui Chemicals Polyurethane Co., Ltd., urethane resin emulsion),
Superflex 870 (Tg: 78 ° C), 800 (Tg: 46 ° C), 150 (Tg: 40 ° C), 420, 460 (Tg: -21 ° C), 470, 610, 700 (above, Dai-ichi Kogyo Seiyaku Co., Ltd.) Product name, polyurethane resin emulsion),
Permarin UA-150 (manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion),
Suncure 2710 (manufactured by Japan Lubrizol, urethane-based resin emulsion),
NeoRez R-9660, R-9637, R-940 (Urethane resin emulsion manufactured by Kusumoto Kasei Co., Ltd.),
ADEKA Bontiter HUX-380,290K (manufactured by ADEKA Corporation, urethane resin emulsion),
Movinyl 966A, Movinyl 7320 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.),
John Krill 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (above, manufactured by BASF),
NK binder R-5HN (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and the like can be mentioned.

The content of the resin emulsion in the treatment liquid in terms of solid content is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, when the total mass of the ink composition is 100% by mass. When the content of the resin emulsion in terms of solid content is within the above range, the fastness of the image becomes good. In addition, the long-term stability of the ink composition is also excellent.

2.1.2. Other components Examples of other components that can be blended in the treatment liquid include components other than the pigments described in the above section of the ink composition, and the blending amount of each component is appropriately within a range that can be ejected by, for example, spraying. Designed to.

2.2. Drying Rate In the printing method of the present embodiment, the step of adhering the treatment liquid to the fabric is performed in a state where the drying rate of the ink composition is less than 90%.

Here, the drying rate refers to the degree of drying of the ink composition at the time when the treatment liquid adheres to the surface of the ink composition, and is the initial state of the ink composition when the drying rate at the time of printing finish is 100%. The rate of decrease in mass of volatile components (water, water-soluble organic solvent, etc.) from (for example, the state in the ink container). That is, for example, when the drying rate is 90%, 90% of the volatile components in the initial state are volatilized (10% of the volatile components remain), and when the drying rate is 20%, the initial state. 20% of the volatile components are volatilized (80% of the volatile components remain). The drying rate can be determined, for example, by adhering the ink composition to the T-shirt fabric, measuring the change in mass with respect to the time after adhering, creating a calibration curve, and using the mass at the time of printing finish as a reference. For example, although not limited to this, when the mass at the time of printing finish is We, the mass immediately after adhesion obtained from the calibration curve is Ws, and the mass Wt after the lapse of time t after adhesion, the drying rate at time t Can also be obtained as {(Wt-We) / (Ws-We)} × 100. In this specification, the mode in which the treatment liquid is adhered to the fabric in a state where the drying rate is less than 90% may be referred to as "wet-on-wet". Further, the mode in which the treatment liquid is attached to the fabric in a state where the drying rate is 90% or more is sometimes referred to as "wet-on-dry" in the present specification.

The step of adhering the treatment liquid to the fabric is performed in a state where the drying rate of the ink composition is less than 90%, so that when the treatment liquid adheres to the fabric, the ink composition and the treatment liquid are appropriately mixed. To. This makes it easier for the first resin to come into contact with the pigment, and the fixability of the pigment can be improved. Further, since the drying rate is less than 90%, the time required for drying the ink composition is unnecessary or very short, so that the time required for producing the printed matter can be shortened, and the printed matter can be produced. Can be efficiently manufactured.

The step of adhering the treatment liquid to the fabric is more preferably performed in a state where the drying rate of the ink composition is less than 80%, more preferably less than 60%, particularly preferably less than 30%, and particularly preferably 20%. It is done below. Further, the lower limit of the drying rate of the ink composition when the step of adhering the treatment liquid to the fabric is performed is 0% (in a non-dried state), preferably 0.05%, more preferably 0.1. %. If the drying rate of the ink composition when the step of adhering the treatment liquid to the fabric is performed is within such a range, the mixing of the ink composition and the treatment liquid is sufficient, and the step of temporarily drying the ink composition. Even if it includes, the time can be shortened.

2.3. Time Interval In the printing method of the present embodiment, the step of adhering the treatment liquid may be started at a time of 1 second or more and 30 seconds or less after the step of adhering the ink composition. After landing on the cloth in the step of adhering the ink composition, the ink composition is dried on the cloth in the state of fine droplets (state in which the surface area is large with respect to the volume). However, if it is 1 second or more and 30 seconds or less, a drying rate of less than 90% can be easily achieved. As a result, the treatment liquid and the ink composition can be mixed, and the fixability of the pigment can be further improved.

2.4. Method other than the inkjet method The step of adhering the treatment liquid to the fabric in the printing method of the present embodiment may be performed by a method other than the inkjet method. Examples of such a method include a method of applying the treatment liquid to the cloth using various sprays, a method of immersing the cloth in the treatment liquid and applying the treatment liquid, a method of applying the treatment liquid to the cloth by a brush or the like. Of these, the non-contact method (spray or immersion) is more preferable in that the image pattern formed by the ink composition is not easily destroyed. Further, a known structure for immersing the spray or cloth to be used can be used, and for example, it can be connected to or built in the above-mentioned inkjet recording device. By providing these in the vicinity of the head for ejecting the ink composition, it is possible to shorten the timing of applying the treatment liquid.

When the step of adhering the treatment liquid to the fabric is performed by the inkjet method, the surface tension and viscosity of the treatment liquid are adjusted by the type and amount of each component. That is, the surface tension of the treatment liquid at 25 ° C. is preferably 10 mN / m or more and 40 mN / m or less, and more preferably 25 mN / m or more and 40 mN / m or less. The viscosity of the treatment liquid at 20 ° C. is preferably 2 mPa · s or more and 15 mPa · s or less, more preferably 2 mPa · s or more and 5 mPa · s or less, and 2 mPa · s or more and 3.6 mPa · s or less. Is more preferable.

3. 3. Action Effect According to the printing method of the present embodiment, the pigment in the ink composition can be fixed to the fabric by the first resin in the treatment liquid, and a printed product having excellent friction fastness and washing fastness can be produced. be able to. Further, since the treatment liquid is adhered to the fabric in a state where the drying rate is low after the ink composition is adhered to the fabric, the ink composition and the treatment liquid are appropriately mixed, so that the fixability is good and the printed material is printed. The time required for production can be shortened, and a printed material having excellent friction fastness and washing fastness can be efficiently manufactured.

Moreover, it is not necessary to add a resin component for fixing to the ink composition, and the viscosity of the ink composition can be kept small. As a result, the ink composition can be stably ejected by the inkjet method. Further, when the treatment liquid is carried out by a method other than the inkjet method, it is not necessary to reduce the viscosity of the treatment liquid to a viscosity suitable for the inkjet method, so that a relatively large amount of the first resin can be blended in the treatment liquid. .. As a result, the fixing (fixing) of the pigment to the fabric can be strengthened, and the fastness of the printed image can be made very high.

4. Modification example 4.1. Second Resin In the printing method of the present embodiment, the second resin may be blended with the ink composition. As the second resin, the same one as the first resin blended in the treatment liquid can be exemplified. Therefore, the description of a specific example of the second resin will be omitted.

When the second resin is contained in the ink composition, the surface tension at 25 ° C. is 10 mN / m or more and 40 mN / m or less from the viewpoint of the balance between the recording quality and the reliability as the ink for inkjet recording. The content is preferably adjusted so as to be 25 mN / m or more and 40 mN / m or less. From the same viewpoint, the viscosity of the ink composition at 20 ° C. is 2 mPa · s or more and 15 mPa · s or less, preferably 2 mPa · s or more and 5 mPa · s or less, and more preferably 2 mPa · s or more and 3.6 mPa · s or less. Adjust the blending amount so that

In this way, even with the ink composition alone, the pigment can be fixed to the cloth by the second resin, and further, the pigment can be fixed to the cloth by the first resin of the treatment liquid. Therefore, it is possible to produce a printed material having further excellent friction fastness and washing fastness. Further, since the first resin is supplied by the treatment liquid, the blending amount of the second resin can be kept small, and the ink composition can easily have a viscosity suitable for the inkjet method. Further, by blending the second resin, the amount of the first resin contained in the treatment liquid can be reduced, and thus the viscosity of the treatment liquid can be suppressed. Therefore, it is possible to obtain an effect that it becomes easy to select a mode in which the treatment liquid is adhered by the inkjet method.

It is more preferable to use the same type of second resin as the first resin. By doing so, the compatibility between the first resin and the second resin is improved, so that the blending amount of the entire resin can be suppressed and the fixability of the pigment can be further improved.

4.2. Dye In the printing method of the present embodiment, a dye may be added to the ink composition. As the dye, although not particularly exemplified, known dyes can be used. By blending the dye into the ink composition, the color development property of the dyed product may be further enhanced.

5. Other Steps In the printing method of the present embodiment, the above-mentioned drying rate can be achieved by, for example, natural drying without performing a heat-drying treatment. However, if necessary, there may be a step of drying the fabric during the step of adhering the ink composition or after the step of adhering the ink composition. Such a step may be performed, for example, by adding a heating unit or a drying unit to the inkjet recording device as appropriate, or by heating and / or drying separately from the inkjet recording device (for example, heat press method, normal pressure). The steam method, the high-pressure steam method, and the thermofix method) may be used. By having the step of drying the ink composition, the drying rate of the ink composition immediately before the step of adhering the treatment liquid can be adjusted.

Further, the printing method of the present embodiment may include a step of adhering the pretreatment liquid before the step of adhering the ink composition. Examples of the pretreatment liquid include those that agglomerate the coloring material (pigment) in the ink composition or thicken the ink composition. The composition of such a pretreatment liquid is not particularly limited, and examples thereof include those containing a metal salt, an organic acid, a cationic compound, and the like.

Such a pretreatment liquid agglomerates or thickens the components of the ink composition, enhances color development by aggregating the coloring material, reduces printing unevenness, and bleeds or bleeds in the image when it adheres to the fabric by thickening. Can be suppressed. As a result, it is possible to suppress printing unevenness of the recorded image. As a method for adhering the pretreatment liquid, for example, any method such as spin coating, spray coating, gravure roll coating, reverse roll coating, bar coating, and inkjet method can be used.

Further, the printing method of the present embodiment may include, for example, corona treatment, atmospheric pressure plasma treatment, frame treatment, ultraviolet irradiation treatment, solvent treatment and the like in addition to the above steps. These treatments can be carried out using a known device. When these treatments are performed, it is more preferable that they are performed before the step of adhering the ink composition. By performing, for example, corona treatment before the step, the adhesion and wettability of the ink composition to the surface of the fabric can be further improved, and the adhesion and abrasion resistance of the pigment may be further improved. ..

5. Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

5.1. Preparation of Ink Composition Each component is placed in a container so as to have the composition shown in Table 1, mixed and stirred with a magnetic stirrer for 2 hours, and then dispersed with a bead mill filled with zirconia beads having a diameter of 0.3 mm. Was thoroughly mixed by performing. Each ink composition was obtained by stirring for 1 hour and then filtering using a 5 μm PTFE membrane filter. The numerical values in Table 1 indicate mass%, and the mass of each ink composition of pure water (ion-exchanged water) is 100% by mass.
It was added so as to be.

なお、表中、シアン顔料分散液は、シアン顔料としてＣ．Ｉ．ピグメントブルー１５：３、６５部をスチレン−アクリル酸系分散樹脂であるジョンクリル６１１（商品名：ＢＡＳＦジャパン株式会社製）３５部、水酸化カリウム１．７０部、イオン交換法と逆浸透法により精製した超純水２５０部を混合して、ジルコニアビーズによるボールミルにて１０時間分散を行い、ガラス繊維ろ紙ＧＡ−１００（商品名：アドバンテック東洋社製）で濾過して粗大粒子を除き、顔料濃度が１５質量％となるように調整したものを用いた。

In the table, the cyanide pigment dispersion liquid is C.I. I. Pigment Blue 15: 3, 65 parts by John Krill 611 (trade name: manufactured by BASF Japan Co., Ltd.), which is a styrene-acrylic acid-based dispersion resin, 1.70 parts of potassium hydroxide, by ion exchange method and reverse osmosis method. 250 parts of purified ultrapure water is mixed, dispersed for 10 hours with a ball mill using zirconia beads, and filtered with glass fiber filter paper GA-100 (trade name: manufactured by Advantech Toyo Co., Ltd.) to remove coarse particles and pigment concentration. Was adjusted to be 15% by mass.

As the second resin, Takelac WS-6021 (Tg: -60 ° C, 40 ° C) (trade name manufactured by Mitsui Chemical Polyurethane Co., Ltd., urethane-based resin emulsion) and Viniblanc 2682 (Tg: -30 ° C) (Nisshin Chemical Industry Co., Ltd. (Product name, acrylic resin emulsion) was used in the formulations shown in the table.

As the components described by the compound names, those purchased as reagents were used. BYK-348 is a siloxane-based surfactant manufactured by Big Chemie Japan.

5.2. Preparation of treatment liquid Each component is placed in a container so as to have the composition shown in Table 2, mixed and stirred with a magnetic stirrer for 2 hours, and then dispersed with a bead mill filled with zirconia beads having a diameter of 0.3 mm. Thoroughly mixed by doing. After stirring for 1 hour, each treatment liquid was obtained by filtering using a 5 μm PTFE membrane filter. The numerical values in Table 2 indicate mass%, and pure water (ion-exchanged water) was added so that the mass of each treatment liquid was 100% by mass.

As the first resin, WS-6021 (Tg: -60 ° C., 40 ° C.) (trade name manufactured by Mitsui Chemicals Polyurethane Co., Ltd., urethane-based resin emulsion) and Viniblanc 2682 (Tg: -30 ° C.), as in the ink composition. (Product name manufactured by Nisshin Chemical Industry Co., Ltd., acrylic resin emulsion) was used in the formulation shown in the table.

５．３．評価試験
５．３．１．染色物の作成
布帛として、市販のＴシャツ生地（商品名「ＨＡＮＥＳヘビーウェイト」、ＨＡＮＥＳ社製、生地色：白、素材：綿１００％）を用意し、布帛に対して、インクジェットプリンター（商品名「ＰＸ−Ｇ９３０」、セイコーエプソン株式会社製）を用いたインクジェット法により、上記のように調製したインク組成物を付着させて画像を印捺した。各実施例、比較例のインクの打ち込み量は表３中に記載の量とした。印捺パターン（画像）は、１４４０×７２０ｄｐｉの解像度、印刷範囲はＡ４サイズとし、Ｄｕｔｙ１００％でベタパターンを印刷することで得られた。また、各実施例、比較例について、表３に記載したタイミングで、スプレー法によって処理液を付着させた。各実施例、比較例の処理液の付着量は表３中に記載の量とした。
なお、比較例１及び比較例２では、処理液の塗布を行わなかった。また、比較例３に関しては、インク組成物の付着後、温風ヒーターで布帛表面を加熱することにより乾燥処理を行い、スプレー法による処理液の付着を行った。なお、比較例３では、乾燥処理を行ったため、処理液の塗布タイミングの測定は行わず、表３中にＮＤと記載した。
また表中、インク乾燥率は、上記印刷と同条件でインク組成物をＴシャツ生地に付着させ、付着後の時間に対する質量の変化を実測して検量線を作成し、係る検量線を用いて、各例のインク組成物塗布後の時間から、読み取った値を記載した。なお、インク組成物をＴシャツ生地に付着させた後にヒートプレスにて１７０℃で１分間加熱乾燥したものを乾燥率１００％とする。
５．３．２．摩擦堅牢性
染色物の摩擦堅牢性試験を、ＪＩＳＬ０８４９摩擦試験機ＩＩ型に準じ、学振式ＡＢ−３０１（テスター産業社製）により実施した（荷重２００ｇ、１００往復）。摩擦布は黒色綿ブロード（綿１００％）を用いた。摩擦後のパターンの表面を目視で観察し、以下の基準で評価して、表３に記載した。
◎：パターンのインクが剥げて下地が見える箇所が全く見られない
○：パターンのインクが剥げて下地が見える箇所がほとんど見られない（パターンの面積に対して１％以下）
△：パターンのインクが剥げて下地が見える箇所が一部見られる（パターンの面積に対して１％超１０％以下）
×：パターンのインクが剥げて下地が見える箇所が全体にみられる（パターンの面積に対して１０％超）。

5.3. Evaluation test 53.1. Creation of dyed products Commercially available T-shirt fabric (trade name "HANES Heavyweight", manufactured by HANES, fabric color: white, material: 100% cotton) is prepared as a fabric, and an inkjet printer (trade name "HANES") is used for the fabric. An image was imprinted by adhering the ink composition prepared as described above by an inkjet method using "PX-G930" (manufactured by Seiko Epson Corporation). The amount of ink applied in each of the examples and comparative examples was the amount shown in Table 3. The printing pattern (image) was obtained by printing a solid pattern with a resolution of 1440 × 720 dpi, a print range of A4 size, and a duty of 100%. Further, for each Example and Comparative Example, the treatment liquid was adhered by the spray method at the timings shown in Table 3. The amount of the treatment liquid adhered to each of the Examples and Comparative Examples was the amount shown in Table 3.
In Comparative Example 1 and Comparative Example 2, the treatment liquid was not applied. Further, in Comparative Example 3, after the ink composition was adhered, the surface of the fabric was heated with a warm air heater to perform a drying treatment, and the treatment liquid was adhered by a spray method. In Comparative Example 3, since the drying treatment was performed, the application timing of the treatment liquid was not measured, and ND was described in Table 3.
Further, in the table, the ink drying rate is determined by adhering the ink composition to the T-shirt fabric under the same conditions as the above printing, measuring the change in mass with respect to the time after adhering, creating a calibration curve, and using the calibration curve. , The values read from the time after application of the ink composition of each example are described. The drying rate is 100% when the ink composition is attached to the T-shirt fabric and then heat-dried at 170 ° C. for 1 minute by a heat press.
5.3.2. Friction fastness The friction fastness test of the dyed product was carried out by the Gakushin type AB-301 (manufactured by Tester Sangyo Co., Ltd.) according to JIS L0849 friction tester type II (load 200 g, 100 reciprocations). A black cotton broadcloth (100% cotton) was used as the friction cloth. The surface of the pattern after rubbing was visually observed and evaluated according to the following criteria, and is shown in Table 3.
⊚: The ink of the pattern is peeled off and the base is not visible at all ○: The ink of the pattern is peeled off and the base is hardly visible (1% or less of the area of the pattern)
Δ: There are some places where the ink of the pattern is peeled off and the base is visible (more than 1% and less than 10% of the area of the pattern).
X: The ink of the pattern is peeled off and the base is visible in the whole area (more than 10% of the area of the pattern).

5.3.3. Washing fastness The washing fastness of the T-shirt after printing was evaluated according to "AATCC612A" and judged as follows.
⊚: Washing fastness is 4th grade or higher ○: Washing fastness is 3rd grade or higher and less than -4th grade Δ: Washing fastness is 2nd grade or higher and lower than 3rd grade ×: Washing fastness is lower than 2nd grade.

5.3.4. Texture The difference in texture between the printed and non-printed areas was evaluated by touch.
◯: The texture of the printed part is almost the same as that of the original fabric Δ: The texture of the printed part feels a little harder ×: The texture of the printed part is clearly hardened.

5.3.5. Head reliability Fill the ink composition and treatment liquid so that they are ejected from multiple nozzle rows of the Epson inkjet printer SC-S30650, and after confirming that all nozzles eject normally, cap the recording head. After standing still at 25 ° C. for one week, a nozzle inspection was performed to confirm the number of non-ejection nozzles out of all 360 nozzles.
◯: The number of non-ejection nozzles was 3 or less Δ: The number of non-ejection nozzles was 4 or more and 10 or less ×: The number of non-ejection nozzles was 10 or more.

5.3.6. Image quality (bleeding)
The bleeding at the boundary between the printed part and the non-printed part was visually observed and evaluated according to the following criteria.
◯: No bleeding △: Slight bleeding ×: Bleeding.

５．４．評価結果
以上の評価結果を表３に記載した。乾燥率が９０％未満で第１樹脂を含有する処理液を塗布した実施例の染色物は、いずれの評価項目も良好であった。また、各実施例では、インク組成物を付着させた後、インク組成物を積極的に乾燥させることなく、３０ｓ以内に処理液を塗布しており、工程全体に要した時間は短かった。

5.4. Evaluation Results The above evaluation results are shown in Table 3. The dyed products of the examples to which the treatment liquid containing the first resin had a drying rate of less than 90% were all good in all evaluation items. Further, in each example, after the ink composition was adhered, the treatment liquid was applied within 30 seconds without actively drying the ink composition, and the time required for the entire process was short.

On the other hand, the dyed product of Comparative Example 1 to which the treatment liquid was not applied had insufficient image fastness. It is considered that this is because the amount of resin is not supplemented by the first resin with respect to the amount of the second resin. Further, the dyed product of Comparative Example 2 to which the treatment liquid was not applied contains a second resin in an amount considered to be sufficient for obtaining toughness only in the ink composition, and the toughness is obtained. However, the reliability of the head deteriorated due to the high viscosity of the ink composition. On the other hand, in Comparative Example 3 in which the drying rate of the ink composition was 90%, the fastness of the image was insufficient. It is considered that this is because even if the treatment liquid is applied in a dry state of the ink composition, the mixture of the two is insufficient and the so-called biting is reduced.
On the other hand, in Example 6 in which the concentration of the second resin in the ink composition was as high as 6% by mass, the reliability of the head was slightly lowered although it was within the permissible range. Further, in Example 7 in which the amount of the first resin in the treatment liquid was small, the robustness was slightly lowered although it was within the permissible range. On the contrary, in Example 8 in which the amount of the first resin in the treatment liquid was large, the toughness was slightly lowered although it was within the permissible range.

Looking at Examples 11 and 12, the relationship between the amount of the ink composition charged and the amount of the treatment liquid charged is that when the amount of the ink composition charged is large and the amount of the treatment liquid charged is small, the robustness There was a tendency for the ink composition to deteriorate, and when the amount of the treatment liquid to be applied was large and the amount of the ink composition to be applied was small, the texture tended to be deteriorated. From this, it is suggested that there is a suitable range for the ratio of the driving amount when balancing the robustness and the texture.

Furthermore, looking at Examples 1 and 13, it was suggested that the urethane-based resin was generally superior when the acrylic resin and the urethane-based resin were compared. Looking at Examples 1 and 14, when a urethane-based resin was used as the second resin of the ink composition, it was more excellent that the first resin of the treatment liquid was the same type of resin as the second resin. It was suggested that the result would be. On the contrary, looking at Examples 13 and 15, when an acrylic resin is used as the second resin of the ink composition, it is more excellent that the first resin of the treatment liquid is a different resin. It was suggested that
The present invention is not limited to the above-described embodiment, and various modifications are possible. For example, the present invention includes a configuration substantially the same as the configuration described in the embodiment (for example, a configuration having the same function, method and result, or a configuration having the same purpose and effect). The present invention also includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. The present invention also includes a configuration that exhibits the same effects as the configuration described in the embodiment or a configuration that can achieve the same object. The present invention also includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (9)

A step of adhering an ink composition containing a pigment to a fabric by an inkjet method,
A step of adhering a treatment liquid containing the first resin to the cloth in a state where the drying rate of the ink composition is less than 90%.
Including
The step of adhering the treatment liquid is performed by a method other than the inkjet method.
A printing method in which the content of the first resin is 3% by mass or more with respect to the total amount of the treatment liquid. In claim 1,
The printing method, wherein the first resin is at least one selected from urethane-based, styrene-acrylic-based, acrylic-based, and vinyl chloride-vinyl acetate-based. In claim 1 or 2,
The printing method, wherein the ink composition contains a second resin. In claim 3,
A printing method in which the glass transition temperature of at least one of the first resin and the second resin is 0 ° C. or lower. In claim 3 or 4,
The printing method, wherein the first resin and the second resin are similar resins. In any one of claims 1 to 5,
The printing method, wherein the step of adhering the treatment liquid is started at a time of 1 second or more and 30 seconds or less after the step of adhering the ink composition. In any one of claims 1 to 6,
The step of adhering the treatment liquid is a printing method performed by spray coating. In any one of claims 1 to 7,
A printing method in which the content of the first resin is 10% by mass or more with respect to the total amount of the treatment liquid. In any one of claims 1 to 8,
A printing method in which the amount of the treatment liquid adhered is 10 g / m ² or more.