Textile ink composition

Abstract

To provide an ink composition for textile printing that improves both material compliance and friction resistance, simultaneously reducing the stiffness of the fabric for textile printing and improving the texture such as touch.SOLUTION: An aspect of the present disclosure relates to an ink composition for textile printing containing: a resin; a pigment; an aqueous medium; and an organic solvent, wherein the resin includes: a first resin having an elongation of 500% or more and 750% or less and a tensile strength of 25 MPa or more and 40 MPa or less; and a second resin having an elongation of 250% or more and 550% or less and a tensile strength of 55 MPa or more and 90 MPa or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a printing ink composition for printing.

Background Art

[0002] Conventionally, as methods for printing on fabrics such as cotton, silk, and polyester, screen printing methods and roller printing methods have been widely used. Since these printing methods require the preparation of screen frames, engraved rollers, etc. for each pattern, they are not suitable for printing in small quantities of multiple varieties. In addition, it is necessary to wash off pastes and the like, and a large amount of wastewater is discharged, so an increase in environmental load has been an issue. On the other hand, the inkjet printing method does not require plate-making operations such as screen frames and engraved rollers, and patterns and colors can be changed simply by changing digital data, so it is suitable for small-quantity production of multiple varieties, and the amount of wastewater discharged can also be significantly reduced, so it has been widely used in recent years.

[0003] Inkjet printing methods have used inkjet inks containing pigments and resins. For example, Patent Document 1 discloses a pigment printing ink composition containing resin particles, water, and an organic solvent. The resin particles have a glass transition temperature of 5°C or lower and are contained at 6.5% by mass or more based on the total amount of the ink composition, and the film elongation is 400% or more and 600% or less, and the film strength is 50 MPa or more.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

[0005] A textile printing ink composition relating to one aspect of the present disclosure comprises a resin, a pigment, an aqueous medium, and an organic solvent, wherein the resin contains a first resin having an elongation of 500% to 750% and a tensile strength of 25 MPa to 40 MPa, and a second resin having an elongation of 250% to 550% and a tensile strength of 55 MPa to 90 MPa. [Modes for carrying out the invention]

[0006] The invention described in Patent Document 1, as mentioned above, states that by incorporating the resin particles described above into a printing ink composition, it is possible to form an image that has good conformability to the stretching and contracting of fabric and excellent abrasion resistance.

[0007] However, in the case of inkjet recording used in textile printing, there is a need not only for improved followability but also for improved friction fastness, and furthermore, for reducing stiffness in the fabric to be printed and improving the texture, such as feel. In this regard, simply using resin particles having the predetermined film elongation and film strength as described above may not be sufficient to obtain adequate friction fastness and texture in printed materials on which images have been formed with the ink composition.

[0008] The embodiments relating to this disclosure will be described in detail below, but this disclosure is not limited to these.

[0009] [Ink composition for textile printing] A textile printing ink composition according to one embodiment of the present disclosure (hereinafter sometimes simply referred to as "ink composition") comprises a resin, a pigment, an aqueous medium, and an organic solvent. The resin comprises a first resin having an elongation of 500% to 750% and a tensile strength of 25 MPa to 40 MPa, and a second resin having an elongation of 250% to 550% and a tensile strength of 55 MPa to 90 MPa. By using such an ink composition, a printed material with excellent dry and wet abrasion fastness can be obtained, and furthermore, the texture of the fabric to be printed is also improved.

[0010] (resin) The resin of this embodiment comprises at least two types of resin. The first resin has an elongation of 500% to 750% and a tensile strength of 25 MPa to 40 MPa. The second resin has an elongation of 250% to 550% and a tensile strength of 55 MPa to 90 MPa.

[0011] By combining a first resin with high elongation and relatively low tensile strength with a second resin with relatively low elongation and high tensile strength, it is believed that the resulting printed material can achieve both abrasion fastness and a desirable texture.

[0012] In this embodiment, "elongation" and "tensile strength" refer to the values ​​measured by the measurement methods described in the examples later.

[0013] For the first resin, a more preferable elongation is 600% or more and 700% or less, and a more preferable tensile strength is 35 MPa or more and 40 MPa or less.

[0014] As the first resin, any resin having the elongation and tensile strength described above can be used without particular limitations, but it is preferable to use one supplied in the form of an aqueous emulsion. Considering the ease of preparing the ink by mixing it with pigments, solvents, and water, and the need to disperse it as uniformly as possible in the ink, it is preferable to add the resin to the ink in the form of a resin emulsion, in which the resin is stably dispersed with water as the dispersion medium.

[0015] Examples of water-dispersible resins that can be used in this embodiment include polyurethane resins, styrene-acrylic resins, silicone resins, polyester resins, and acrylic resins. Copolymers obtained by copolymerizing two or more of the above resins, such as styrene-acrylic resin-polyester resin copolymers and styrene-acrylic resin-urethane resin copolymers, can also be used.

[0016] Furthermore, the above resin may have reactive functional groups, and may also be a polymer containing a crosslinking agent. This is thought to result in superior adhesion, as a portion of the resin undergoes crosslinking and strong bonding with the fabric during transfer, leading to an increase in molecular weight or a curing reaction.

[0017] Furthermore, increasing the amount of fixing resin added to improve the adhesion stability of the ink to the fabric may reduce the flexibility of the fabric to which the image has been transferred, resulting in a stiff texture and potentially degrading the feel. Therefore, it is preferable to use a resin that has a molecular structure that retains flexibility even after curing, such as urethane resin.

[0018] There are no particular limitations on the specific urethane resin, but examples include polyurethane resins obtained by reacting polyols and polyisocyanates. More specifically, polymers can be used that combine polyols such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, poly(ethylene adipate), poly(diethylene adipate), poly(propylene adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), poly-ε-caprolactone, poly(hexamethylene carbonate), and silicone polyols with isocyanates such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, and tetramethylxylylene diisocyanate, bonded together by urethane linkage, or block copolymers, random copolymers, graft copolymers, etc., of these polymers.

[0019] As the styrene-acrylic resin, one or more selected from styrene-(meth)acrylic acid copolymer and styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer can be used in combination. As the above (meth)acrylic acid ester, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, phenol EO modified (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. can be used.

[0020] As the silicone resin, modified silicone oils of side-chain type, single-ended type, double-ended type, and side-chain double-ended type can be used.

[0021] As polyester resins, polymers formed by ester bonding of divalent carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, sodium sulfisoisophthalate, succinic acid, adipic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, and dimer acid, and trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyrrolimetic acid, and divalent alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, polytetraethylene glycol, 1,4-cyclohexanedimethanol, and ethylene oxide adducts of bisphenol A, and trivalent or higher polyvalent alcohols such as trimethylolpropane and pentaerythritol, or block copolymers, random copolymers, and graft copolymers thereof can be used.

[0022] In the second resin, a more preferable elongation is 250% or more and 300% or less, and a more preferable tensile strength is 60 MPa or more and 90 MPa or less.

[0023] As the second resin, any resin having the above-described elongation and tensile strength can be used without particular limitation. Specifically, various resins listed as the first resin above can be used.

[0024] The first resin and the second resin may be the same type of resin or different types of resins. When the same type of resin is used for the first resin and the second resin, the compatibility between the resins can be enhanced, and a uniform coating film can be obtained.

[0025] In the resin contained in the ink composition of the present embodiment, the weight ratio of the first resin to the second resin (second resin / first resin) is preferably about 0.6 to 1.7. Thereby, it is possible to achieve both friction resistance and texture, and it is considered to be particularly excellent in dry friction resistance. A more preferable range of the weight ratio is 0.8 or more and 1.2 or less.

[0026] In addition, as long as the resin of the present embodiment contains the first resin and the second resin, another resin may be further contained in addition to the first resin and the second resin as long as the effects of the present disclosure are not inhibited.

[0027] From the viewpoint of obtaining high friction resistance, the content of the resin (total of the first resin and the second resin) in the ink composition of the present embodiment is preferably 6% by mass or more and 9% by mass or less with respect to the entire ink composition. A more preferable content is 7% by mass or more and 8% by mass or less.

[0028] (Pigment) For the pigment blended in the ink composition of the present embodiment, for example, a dispersible pigment present in a dispersed state in water can be used. From the viewpoint of obtaining an ink excellent in image density, hue, and color stability, the volume median diameter (D50 The wavelength is preferably 30 nm to 250 nm, and more preferably 70 nm to 160 nm.

[0029] In this specification, the median diameter (D 50 The measured value is the median diameter, measured using a laser diffraction / scattering particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.).

[0030] In this embodiment, conventionally known organic and inorganic pigments can be used as pigments. Examples include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perylene pigments, anthraquinone pigments, quinacridone pigments, dioxandine pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye lakes such as basic dye-type lakes and acid dye-type lakes; organic pigments such as nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments; and inorganic pigments such as carbon black.

[0031] More specific examples of pigments include CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 48:1, CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 139, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 222, and others, which are used for magenta or red.

[0032] Examples of pigments for orange or yellow include CI Pigment Orange 31, CI Pigment Orange 43, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 17, CI Pigment Yellow 74, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 128, CI Pigment Yellow 138, and others.

[0033] Examples of pigments for green or cyan include CI Pigment Blue 15, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 16, CI Pigment Blue 60, and CI Pigment Green 7.

[0034] In this embodiment, the pigment content is preferably 1% by mass or more and 12% by mass or less, and more preferably 1% by mass or more and 7% by mass or less, based on the total weight of the ink composition. A pigment content of 1% by mass or more improves the image density of the resulting recording. Furthermore, a pigment content of 12% by mass or less yields a highly fluid ink.

[0035] Furthermore, it is preferable that the ink composition of this embodiment contains an anionic pigment. As a result, the cationic polymer contained in the processing solution used in combination with the ink composition and the anionic pigment undergo an electrical reaction and aggregation on the surface of the material to be recorded, thereby suppressing the penetration of the resin contained in the ink into the printed material. In other words, it is possible to prevent the resin from penetrating into the gaps between fibers and binding the fibers together, thereby improving the texture (feel, etc.) of the fabric to be printed.

[0036] In this embodiment, it is preferable to disperse the pigment in a dispersion containing a pigment dispersion resin and use it as a pigment dispersion.

[0037] Examples of pigment dispersion resins that can be used in this embodiment include alkali-soluble resins such as styrene-acrylic acid copolymer, styrene-acrylic acid-alkyl acrylate copolymer, styrene-maleic acid copolymer, styrene-maleic acid-alkyl acrylate copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-alkyl acrylate copolymer, styrene-maleic acid half-ester copolymer, vinylnaphthalene-acrylic acid copolymer, and vinylnaphthalene-maleic acid copolymer. If necessary, these may be used individually or in combination of two or more.

[0038] (aqueous medium) The aqueous medium contained in the ink composition of this embodiment is a medium mainly composed of water. The aqueous medium may function as a solvent or as a dispersion medium. Specific examples of the aqueous medium include water or a mixture of water and a polar solvent. Examples of polar solvents contained in the aqueous medium include methanol, ethanol, isopropyl alcohol, butanol, and methyl ethyl ketone.

[0039] (Organic solvents) The organic solvent contained in the ink composition of this embodiment is not particularly limited, but examples include polyols and glycol ethers.

[0040] In particular, the inclusion of a polyol in the ink composition is preferable because it allows for a suitable adjustment of the ink's viscosity. Preferred polyols in the ink composition are diols or triols. Examples of diols include glycol compounds, more specifically, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. An example of a triol is glycerin.

[0041] (Additives and manufacturing methods) The ink composition according to this embodiment may contain surfactants in addition to the essential components (resin, pigment, aqueous medium, organic solvent) described above. Examples of preferred surfactants include acetylene glycol-based surfactants and silicone-based surfactants.

[0042] The amount of the surfactant in the ink composition is preferably about 0.01 to 3.0% by mass, and more preferably 0.1 to 1.0% by mass, relative to the total amount of the ink composition.

[0043] Furthermore, the ink composition of this embodiment may optionally contain known additives (more specifically, dissolution stabilizers, drying inhibitors, antioxidants, viscosity modifiers, pH adjusters, and antifungal agents, etc.).

[0044] When an ink composition contains a pH adjusting agent, the pH adjusting agent is not particularly limited, but examples include sodium hydroxide, triethanolamine, dimethylaminoethanol, etc. The inclusion of a pH adjusting agent in the ink composition makes it possible to adjust the ink composition to a desired pH.

[0045] The pH adjusting agent content in the ink composition of this disclosure is preferably 0.01% by mass or more and 1% by mass or less, and more preferably 0.05% by mass or more and 0.2% by mass or less. However, the pH adjusting agent content is not limited to the above range and may be adjusted as appropriate, for example, according to the desired pH of the ink composition.

[0046] The ink composition used in this embodiment is manufactured, for example, by mixing a resin, a pigment, an aqueous medium, an organic solvent, and optionally added components (e.g., a surfactant) using a stirrer. The mixing time is, for example, 1 minute to 30 minutes. After mixing, the mixture is centrifuged to remove coarse particles such as foreign matter and debris, and then filtered to remove fine particles, thereby obtaining the ink composition of this embodiment.

[0047] The ink composition obtained according to this embodiment has its physical properties adjusted for inkjet printing, and is therefore particularly suitable for use in inkjet textile printing, but can also be used in textile printing machines other than inkjet printers. [Examples]

[0048] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited in any way by these examples.

[0049] [Example 1] (Preparation of pigment dispersion) A stirrer, nitrogen inlet tube, condenser, and dropping funnel were set up in a 1000 mL four-necked flask. Next, 100 g of isopropyl alcohol and 300 g of methyl ethyl ketone were added to the flask. The contents of the flask were then heated under reflux at 70°C while bubbling with nitrogen gas.

[0050] Furthermore, 40g of styrene (ST), 10g of methacrylic acid (MAA), 10g of butyl acrylate (BA), 40g of methyl methacrylate (MMA), and 0.4g of azobisisobutyronitrile (AIBN) were mixed to obtain a solution. The obtained solution was then placed into a dropping funnel. Subsequently, the solution in the dropping funnel was added dropwise to the contents of the flask under reflux over a period of 2 hours. After the addition was complete, the contents of the flask were heated under reflux for a further 6 hours.

[0051] Next, 50 ml of methyl ethyl ketone containing 0.2 g of AIBN was added dropwise to the flask over 15 minutes. After the addition was complete, the contents of the flask were heated under reflux for a further 5 hours. As a result, a styrene-acrylic acid resin with a mass-average molecular weight (Mw) of 20,000 and an acid value of 100 mg KOH / g was obtained.

[0052] In a 0.6 L vessel of a media-type disperser ("DYNO®-MILL" manufactured by Willy E. Bakkofen (WAB) GmbH), 15 parts by mass of cyan pigment ("Lionol® Blue FG-7330" manufactured by Toyo Color Co., Ltd., component: copper phthalocyanine, color index: pigment blue 15:3), 6 parts by mass of resin, 0.5 parts by mass of 1,2-octanediol, and 78.5 parts by mass of water (deionized water) were placed. In addition, the amount of sodium hydroxide (NaOH) necessary to neutralize the resin was added to the vessel. The pigment content in the resulting pigment dispersion was 14.5% by mass.

[0053] In the neutralization of the resin described above, an aqueous NaOH solution was added to the vessel so that the pH of the contents of the vessel became 8. Specifically, an aqueous NaOH solution equal to 1.1 times the mass of the neutralization equivalent was added to the vessel. The mass of Na to be added to the vessel was calculated based on the mass of the resin. The mass of water to be added to the vessel was calculated based on the sum of the mass of water contained in the aqueous NaOH solution and the mass of water produced in the neutralization reaction.

[0054] Next, media (zirconia beads with a diameter of 0.5 mm) was filled into the vessel of the disperser to 70% by volume relative to the vessel's capacity. Subsequently, the contents of the vessel were kneaded for 240 minutes using the disperser filled with media at a temperature of 10°C and a peripheral speed of 8 m / s. As a result, a pigment dispersion containing a large number of pigment particles was obtained. The median diameter (D) of the pigment particles contained in the pigment dispersion was... 50 The median diameter (D) of the pigment particles contained in the pigment dispersion was 100 nm. 50 The measurement of the particle size distribution was performed using a dynamic light scattering particle size distribution analyzer (Sysmex Corporation's "Zetasizer Nano") as the measuring device, with the pigment dispersion diluted 300 times with deionized water as the measurement target.

[0055] (Mixing of pigment dispersion with other components) 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of urethane resin "Hydran AP-10" (manufactured by DIC Corporation, tensile strength 36 MPa, elongation 520%) as the first resin, 4 parts by mass of urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were mixed uniformly using a stirrer ("Three One Motor BL-600" manufactured by Shinto Kagaku Co., Ltd.) at a rotation speed of 400 rpm. Subsequently, the resulting mixture was filtered using a filter with a pore size of 5 μm to remove foreign matter and coarse particles from the mixture. As a result, the ink composition of Example 1 was obtained.

[0056] [Example 2] The ink of Example 2 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex (SF) 460" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 25 MPa, elongation 750%) as the first resin, 4 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol (registered trademark) 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0057] [Example 3] The ink of Example 3 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 4 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0058] [Example 4] The ink of Example 4 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 4 parts by mass of the urethane resin "Takelac W-6110" (manufactured by Mitsui Chemicals, Inc., tensile strength 55 MPa, elongation 550%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0059] [Example 5] The ink of Example 5 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 5 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 3 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0060] [Example 6] The ink of Example 6 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 3 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 5 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0061] [Example 7] The ink of Example 7 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 4 parts by mass of the urethane resin "Takelac W-6020" (manufactured by Mitsui Chemicals, Inc., tensile strength 60 MPa, elongation 480%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0062] [Example 8] An ink for Example 8 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 5.3 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 2.7 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0063] [Example 9] The ink of Example 9 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 2.9 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 5.1 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0064] [Example 10] The ink of Example 10 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 3 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 3 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol (registered trademark) 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 43.5 parts by mass of ion-exchanged water were used.

[0065] [Example 11] An ink for Example 11 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4.5 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 4.5 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 40.5 parts by mass of ion-exchanged water were used.

[0066] [Example 12] An ink for Example 12 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 2.5 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 2.5 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 44.5 parts by mass of ion-exchanged water were used.

[0067] [Example 13] An ink for Example 13 was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 5 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 5 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 39.5 parts by mass of ion-exchanged water were used.

[0068] [Comparative Example 1] Comparative Example 1 ink was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of urethane resin "Takelac W-6355" (manufactured by Mitsui Chemicals, Inc., tensile strength 35 MPa, elongation 450%) as the first resin, 4 parts by mass of urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0069] [Comparative Example 2] Comparative Example 2 ink was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex 460S" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 30 MPa, elongation 790%) as the first resin, 4 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0070] [Comparative Example 3] Comparative Example 3 ink was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex E-4800" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 19 MPa, elongation 720%) as the first resin, 4 parts by mass of the urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0071] [Comparative Example 4] Comparative Example 4 ink was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of urethane resin "Takelac WS-5000" (manufactured by Mitsui Chemicals, Inc., tensile strength 50 MPa, elongation 500%) as the first resin, 4 parts by mass of urethane resin "ETERNACOLL UW-1527DF" (manufactured by Ube Industries, Ltd., tensile strength 90 MPa, elongation 270%) as the second resin, 0.5 parts by mass of nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0072] [Comparative Example 5] Comparative Example 5 ink was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 4 parts by mass of the urethane resin "Takelac WPB-341" (manufactured by Mitsui Chemicals, Inc., tensile strength 60 MPa, elongation 50%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0073] [Comparative Example 6] Comparative Example 6 ink was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 4 parts by mass of the urethane resin "Takelac WS-5984" (manufactured by Mitsui Chemicals, Inc., tensile strength 55 MPa, elongation 600%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0074] [Comparative Example 7] Comparative Example 7 ink was obtained in the same manner as in Example 1, except that 20 parts by mass of pigment dispersion, 30 parts by mass of propylene glycol, 4 parts by mass of the urethane resin "Superflex 470" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., tensile strength 40 MPa, elongation 640%) as the first resin, 4 parts by mass of the urethane resin "Takelac WS-5000" (manufactured by Mitsui Chemicals, Inc., tensile strength 50 MPa, elongation 500%) as the second resin, 0.5 parts by mass of a nonionic surfactant ("Surfinol® 420" manufactured by Nisshin Chemical Industry Co., Ltd., component: glycol compound having an acetylene group), and 41.5 parts by mass of ion-exchanged water were used.

[0075] The compositions of the ink compositions of the examples and comparative examples obtained above are summarized in Table 1.

[0076] [Table 1]

[0077] (Measurement of tensile strength and elongation) The tensile strength and elongation of each resin used in the examples and comparative examples were measured as follows.

[0078] First, each resin was applied to a PET film so that the film thickness after drying would be 500 μm, and then dried at 25°C and 50% RH for 12 hours. Next, it was dried at 150°C for 20 minutes, then peeled off the sheet to create a resin film.

[0079] Next, the elongation of the obtained resin film was measured using a tensile testing machine at a measurement temperature of 20°C and a measurement speed of 200 mm / min. Elongation was measured by stretching the resin film and measuring the length stretched when the resin film broke, and the elongation was expressed as a percentage.

[0080] Furthermore, the tensile strength of the resin was obtained by measuring the tensile strength at the time of fracture.

[0081] In this evaluation, tensile testing was performed using a machine such as the "Tensilon Universal Tester RTC-1210A" manufactured by Orientec Co., Ltd.

[0082] Table 2 summarizes the tensile strength and elongation of each resin used.

[0083] [Table 2]

[0084] <Evaluation Test> The following evaluation tests were performed using the ink compositions obtained in the above examples and comparative examples.

[0085] (Texture evaluation) The evaluation was conducted using an image forming system (line head-equipped inkjet recording device, manufactured by Kyocera Document Solutions Inc.) under conditions of 25°C and 50% RH. The recording medium used was 120g / m² polyester tropical fiber. 2 (Manufactured by Toray Industries, Inc.) was used.

[0086] A solid image measuring 28 cm x 3 cm was formed by ejecting 35 pL of ink per pixel from the recording head onto the recording medium. The printed evaluation image was then dried at 160°C for 3 minutes.

[0087] The fabric and printed image were folded in half, and the height of the fabric was measured and recorded when bent perpendicular to the vertical direction. The texture was then evaluated using the following criteria as an evaluation value.

[0088] Evaluation criteria: ○: Folding height is less than 26mm △: Folding height is 26mm~27mm ×: Folding height is 28mm or more

[0089] (Friction hardness evaluation) The evaluation was conducted using an image forming system (line head-equipped inkjet recording device, manufactured by Kyocera Document Solutions Inc.) under conditions of 25°C and 50% RH. The recording medium used was 120g / m² polyester tropical fiber. 2 (Manufactured by Toray Industries, Inc.) was used.

[0090] A solid image measuring 28 cm x 3 cm was formed by ejecting 35 pL of ink per pixel from the recording head onto the recording medium. The printed evaluation image was then dried at 160°C for 3 minutes.

[0091] Subsequently, the printed materials were evaluated according to the dry and wet tests of the friction test machine type II (JSPS type) described in JIS L-0849:2013 (Test method for color fastness to friction).

[0092] The friction cloth used was cotton cloth (Kanakin No. 3), and friction was measured using a friction testing device (product name: RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). After friction, three areas with high color transfer density were visually identified from the areas of color transfer on the cotton cloth, and the color was measured using a colorimeter (product name: Portable Reflectance Densitometer RD-19 (manufactured by Gretag Macbeth)). The degree of color transfer, i.e., friction fastness, was evaluated by the average value of the optical density (cyan). In this test, a dry friction fastness rating of C or higher and a wet friction fastness rating of E or higher were considered to be practical.

[0093] Evaluation criteria: A: The optical density (cyan) of color transfer on the cotton fabric after friction is less than 0.15. B: The optical density (cyan) of color transfer on the cotton fabric after friction is 0.15 or higher and less than 0.20. C: The optical density (cyan) of color transfer on cotton fabric after friction is 0.20 or higher and less than 0.25. D: The optical density (cyan) of color transfer on the cotton fabric after friction is 0.25 or higher and less than 0.30. E: The optical density (cyan) of color transfer on cotton fabric after friction is 0.30 or higher and less than 0.35. F: The optical density (cyan) of color transfer on the cotton fabric after friction is 0.35 or higher.

[0094] The results of the above evaluation tests are summarized in Table 3.

[0095] [Table 3]

[0096] (Consideration) The results in Table 3 confirm that using the ink composition of this disclosure yields printed materials with good texture and excellent rubbing fastness. In particular, a comparison of Examples 5-6 and Examples 8-9 shows that when the ratio of the second resin to the first resin is 0.6 or higher, the dry rubbing fastness is superior. It was also found that when the resin ratio is 1.7 or lower, the dry rubbing fastness is superior.

[0097] Furthermore, a comparison of Examples 10-11 and Examples 12-13 revealed that if the resin content is 6% by mass or more relative to the total ink composition, the dry friction fastness is superior. It was also found that if the resin content is 9% by mass or less relative to the total ink composition, the texture is superior.

[0098] On the other hand, when using the ink compositions of Comparative Examples 1 to 7, in which at least one of the first and second resins contained in the resin did not satisfy the provisions of the present invention, the standards for at least one of the evaluation tests of texture, dry rubbing fastness, and wet rubbing fastness were not met.

Claims

1. It comprises a resin, a pigment, an aqueous medium, and an organic solvent. The aforementioned resin contains a first resin having an elongation of 500% or more and 750% or less, and a tensile strength of 25 MPa or more and 40 MPa or less, and a second resin having an elongation of 250% or more and 300% or less, and a tensile strength of 55 MPa or more and 90 MPa or less. A textile printing ink composition wherein the resin content is 6% by mass or more and 9% by mass or less of the total ink composition.

2. The ink composition for textile printing according to claim 1, wherein the tensile strength of the second resin is 60 MPa or more and 90 MPa or less.

3. The ink composition for textile printing according to claim 1, wherein the first resin and the second resin are polyurethane resins.

4. A textile printing ink composition according to any one of claims 1 to 3, used for inkjet textile printing.

5. Equipped with a recording head that ejects ink onto the recording medium, The ink is the ink composition for printing described in claim 4, wherein the ink is an inkjet printing machine.

6. Includes an ink ejection step of ejecting ink onto a recording medium, The ink is the ink for printing described in claim 4, wherein the ink is an ink composition for printing described in claim 4, in an inkjet printing method.

Images