JP2017190370A - Inkjet ink composition, and printing method - Google Patents

Abstract

An inkjet ink composition is provided that can suppress the generation of aggregates at a high level while containing resin particles.
An ink-jet ink composition comprising a colorant, water, an organic solvent, and resin particles, the resin particles comprising a resin having an elastic modulus of 400 MPa or more and 1000 MPa or less, comprising pyrrolidones and glycol monoethers. The inkjet ink composition whose total content is 1.5 mass% or less with respect to the total amount of the said inkjet ink composition.
[Selection figure] None

Description

  The present invention relates to an inkjet ink composition and a textile printing method.

  The ink jet recording method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields. Among them, various studies have been made on obtaining a more stable and high-quality recorded matter.

  For example, in Patent Document 1, for the purpose of providing an ink for ink-jet printing, an ink-jet printing apparatus and an ink-jet printing method that are excellent in storage stability while suppressing the generation of aggregates, a pigment, a resin, A 2-pyrrolidone-based solvent, having a pH of 9.2 or more and 10.5 or less, used for recording on a fabric, and the film elongation of the resin may be 400% or more and 1200% or less, An ink for ink jet textile printing in which the resin may be a urethane resin is disclosed.

JP 2014-148564 A

  Here, the ink as disclosed in Patent Document 1 contains a resin for fixing the pigment to the recording medium, and a 2-pyrrolidone-based solvent for suppressing the generation of aggregates due to the resin. Is further contained. As a result, the ink has excellent storage stability while suppressing the generation of aggregates, but at higher levels, it may not be sufficient to suppress the generation of aggregates in the ink.

  Accordingly, the present invention has been made to solve at least a part of the above-described problems, and an object of the present invention is to provide an ink-jet ink composition capable of suppressing the generation of aggregates at a high level while containing resin particles. And

  As a result of intensive studies to solve the above problems, the inventors of the present invention include a coloring material, water, an organic solvent, and resin particles, and the elastic modulus of the resin contained in the resin particles is within a predetermined range, and pyrrolidone The present invention has been completed by finding that the use of an ink-jet ink composition having a total content of alcohols and glycol monoethers of not more than a predetermined value can suppress the generation of aggregates at a high level.

  That is, the present invention is an ink-jet ink composition comprising a coloring material, water, an organic solvent, and resin particles, wherein the resin particles comprise a resin having an elastic modulus of 400 MPa or more and 1000 MPa or less, The inkjet ink composition has a total content of pyrrolidones and glycol monoethers of 1.5% by mass or less based on the total amount of the inkjet ink composition. The reason why such an inkjet ink composition can solve the problems of the present invention is considered as follows. However, the factor is not limited to this. That is, the ink-jet ink composition according to the present invention mainly includes resin particles containing a resin having an elastic modulus of 400 MPa or more, and the total content of pyrrolidones and glycol monoethers is 1.5% by mass or less. As a result, even when water or an organic solvent evaporates with time and the composition of the ink composition changes, a member that comes into contact with the ink composition (for example, a container that contains the ink composition or a discharge container) The generation of aggregates can be suppressed due to the resin particles being less likely to form a coating on the discharge nozzle).

  Moreover, in the inkjet ink composition according to the present invention, the resin particles are preferably particles including one or more selected from the group consisting of urethane resins and (meth) acrylic resins, and include a softening agent. Further preferably, the acid value of the resin particles is preferably 60 mgKOH / g or less, the resin particles are preferably self-emulsifying resin particles, and the average particle diameter of the resin particles is 10 nm to 200 nm. And preferably used in a method for recording the inkjet ink composition on a recording medium containing a fabric.

  Furthermore, the textile printing method of the present invention has a step of recording the inkjet ink composition according to the present invention on a recording medium containing a fabric.

It is a flowchart which shows an example of the textile printing method of this embodiment.

  Hereinafter, an embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to this, and the gist thereof is described below. Various modifications are possible without departing from the scope. In the present specification, “(meth) acrylic resin” means both acrylic resin and methacrylic resin corresponding thereto.

  In this specification, “printing” refers to recording (printing) ink on a recording medium including a fabric. “Inkjet textile printing” refers to recording (printing) ink on a recording medium including a fabric using an inkjet method, and is a kind of inkjet recording. “Recorded matter” refers to an image formed by recording ink on a recording medium including a fabric.

[Ink composition]
The ink-jet ink composition of the present embodiment (hereinafter also simply referred to as “ink composition”) includes a color material, water, an organic solvent, and resin particles. The resin particles include a resin having an elastic modulus of 400 MPa to 1000 MPa. Furthermore, the total content of pyrrolidones and glycol monoethers is 1.5% by mass or less with respect to the total amount (100% by mass) of the ink composition. The reason why such an ink composition can suppress the generation of aggregates at a high level is considered as follows. However, the factor is not limited to this. That is, the ink composition of the present embodiment mainly includes resin particles containing a resin having an elastic modulus of 400 MPa or more, and the total content of 2-pyrrolidones and glycol monoethers is 1.5% by mass or less. As a result, even when water or an organic solvent evaporates with time and the composition of the ink composition changes, a member that comes into contact with the ink composition (for example, a container for containing the ink composition or a discharge container) The generation of aggregates can be suppressed due to the resin particles becoming difficult to form a coating film on the discharge nozzle). In addition, the ink composition of the present embodiment is excellent in ejection stability, and clogging generated in the ejection nozzle is easily resolved (excellent clogging recovery property).

<Color material>
The color material of this embodiment can contain a pigment. Although it does not specifically limit as a pigment, For example, the following are mentioned.

  The carbon black used for the black ink is not particularly limited. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. (Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (above, Columbia Carbon, Carbon 1 Rubbi 400, Carbon Co. Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (Cabot Corp. CA Kol. , Color B lack FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A , Special Black 4 (manufactured by Degussa).

  Although it does not specifically limit as a pigment used for white ink, For example, C.I. I. Pigment white 6, 18, 21, titanium oxide, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, white hollow resin particles and polymer particles.

  Although it does not specifically limit as a pigment used for yellow ink, For example, 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.

  Although it does not specifically limit as a pigment used for a magenta ink, For example, 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: 2, 48: 5, 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, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50.

  Although it does not specifically limit as a pigment used for cyan ink, For example, 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, C.I. I. Bat Blue 4, 60, and C.I. I. Direct Blue 199 is exemplified.

  The pigments other than those described above are not particularly limited. I. Pigment green 7,10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63.

  In the ink composition, the content of the coloring material is preferably 0.2% by mass or more and 10% by mass or less, more preferably 1.0% by mass or more and 7% by mass with respect to the total amount (100% by mass) of the ink composition. It is 0.0 mass% or less, More preferably, it is 2.0 mass% or more and 5.0 mass% or less. When the content of the color material is within the above range, the color developability, ejection stability, and clogging recovery tend to be further improved.

<Water>
The ink composition of this embodiment contains water. Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the aggregated liquid is stored for a long period of time. This tends to improve the storage stability.

<Organic solvent>
The ink composition of this embodiment contains an organic solvent. An organic solvent will not be specifically limited if it is an organic solvent which can be used with water. The total content of pyrrolidones and glycol monoethers, which are organic solvents, is 1.5% by mass or less, preferably 1.0% by mass with respect to the total amount (100% by mass) of the ink composition. Or less, more preferably 0.5% by mass or less. In particular, it is preferable that pyrrolidones and glycol monoethers are not contained in the ink composition from the viewpoint of further suppressing the generation of aggregates. By preventing the total content of 2-pyrrolidones and glycol monoethers from exceeding 1.5% by mass, the generation of aggregates can be suppressed at a high level. This factor is inferred as follows (however, the factor is not limited to this). The ink composition contains pyrrolidones and / or glycol monoethers, whereby the pyrrolidone or glycol monoether resin particles promote the dissolution of the resin adhering to the recording medium. A printed matter having excellent properties can be obtained. However, in the conventional ink composition, when the total content of pyrrolidones and glycol monoethers exceeds 1.5% by mass, the composition of the ink composition changed due to evaporation of water and organic solvents over time. In some cases, the generation of aggregates cannot be suppressed at a high level. On the other hand, the ink composition of the present embodiment can suppress the generation of aggregates at a high level when the total content of pyrrolidones and / or glycol monoethers is 1.5% by mass or less.

  Although it does not specifically limit as a kind of organic solvent, For example, a cyclic nitrogen compound, an aprotic polar solvent, a monoalcohol, an alkyl polyol, and glycol ether are mentioned. As the organic solvent of this embodiment, various organic solvents can be appropriately selected from these organic solvents so that the total content of pyrrolidones and glycol monoethers is 1.5% by mass or less. .

  The aprotic polar solvent is not particularly limited, and examples thereof include a cyclic ketone compound, a chain ketone compound, and a chain nitrogen compound. Typical examples of the cyclic nitrogen compound and the aprotic polar solvent include solvents of pyrrolidones, imidazolidinones, sulfoxides, lactones, amide ethers, and imidazoles. The pyrrolidone is not particularly limited as long as it has a pyrrolidone skeleton, and examples thereof include 2-pyrrolidone, N-alkyl-2-pyrrolidone, and 1-alkyl-2-pyrrolidone. Examples of imidazolidinones include 1,3-dimethyl-2-imidazolidinone, sulfoxides such as dimethyl sulfoxide, lactones such as γ-butyrolactone, and imidazoles such as imidazole, 1- Examples include methylimidazole, 2-methylimidazole, and 1,2-dimethylimidazole. Among these, it is preferable that 2-pyrrolidone is not contained more than 1.5% by mass with respect to the total amount (100% by mass) of the ink composition in terms of suppressing the generation of aggregates at a high level.

  Although it does not specifically limit as monoalcohol, For example, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pen Examples include butanol, 3-pentanol, and tert-pentanol.

  Although it does not specifically limit as an alkyl polyol, For example, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol (1,2-propanediol), dipropylene glycol, 1,3-propylene glycol (1,3-propane) Diol), isobutylene glycol (2-methyl-1,2-propanediol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 1 , 2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1 , 7-Heptanediol and 1,8-octanediol And the like.

  Although it does not specifically limit as glycol ether, For example, glycol diethers and glycol monoethers are mentioned.

  Specific examples of the glycol diether include, but are not limited to, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol Ethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol Methyl ether, and, dipropylene glycol diethyl ether.

  Specific examples of the glycol monoether include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, Ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether and the like. Among these, triethylene glycol monobutyl ether does not contain more than 1.5% by mass with respect to the total amount (100% by mass) of the ink composition in terms of suppressing the generation of aggregates at a high level. preferable.

  The content of the organic solvent is preferably 5.0% by mass to 50% by mass and more preferably 10% by mass to 30% by mass with respect to the total amount (100% by mass) of the ink composition. When the content of the organic solvent is 50% by mass or less, the drying property of the ink composition attached to the recording medium tends to be further improved. Moreover, when the content of the organic solvent is 5.0% by mass or more, the ejection stability of the ink composition tends to be ensured.

<Resin particles>
The resin particles of the present embodiment (hereinafter also referred to as “resin dispersion” or “resin emulsion”) are particles containing a resin (hereinafter also referred to as “specific resin”) having an elastic modulus of 400 MPa to 1000 MPa. is there.

  The elastic modulus of the specific resin is 400 MPa or more and 1000 MPa or less, preferably 500 MPa or more and 900 MPa or less, more preferably 550 MPa or more and 800 MPa or less, and further preferably 600 MPa or more and 750 MPa or less. When the elastic modulus is 400 MPa or more, the generation of aggregates due to the aggregation of the resin can be suppressed. Moreover, when the elastic modulus is 1000 MPa or less, a printed matter excellent in friction fastness can be obtained. In order to obtain a resin having an elastic modulus of 400 MPa or more and 1000 MPa or less, a resin having an elastic modulus within the above range may be selected from the types of resins preferable as the specific resin described later. The elastic modulus of the specific resin can be measured by a tensile test after using the resin as a resin film. More specifically, the elastic modulus is measured by a method described in Examples described later.

  The 100% modulus of the specific resin is preferably 20 MPa or more and 100 MPa or less, more preferably 25 MPa or more and 75 MPa or less, further preferably 30 MPa or more and 60 MPa or less, and still more preferably 40 MPa or more and 55 MPa or less. When the 100% modulus is 20 MPa or more, the generation of aggregates due to the aggregation of the resin tends to be further suppressed. Further, when the 100% modulus is 100 MPa or less, there is a tendency to obtain a printed product having further excellent friction fastness. In order to obtain a resin having a 100% modulus within the above range, a resin having a 100% modulus within the above range may be selected from the types of resins preferable as the specific resin described later. The 100% modulus of the specific resin can be measured by a tensile test after using the resin as a resin film. More specifically, the 100% modulus is measured by the method described in Examples described later.

  The resin particles of the present embodiment may be self-dispersing resin particles (self-dispersing resin particles) into which hydrophilic components necessary for stable dispersion in water are introduced, or water may be added by using an external emulsifier. Resin particles that are dispersible may also be used. However, the resin particles are preferably a self-emulsifying resin dispersion from the viewpoint of not inhibiting the reaction with the polyvalent metal compound that can be contained in the recording medium described later.

  Specific resins include, for example, (meth) acrylic resins, styrene acrylic resins, fluorene resins, urethane resins, polyolefin resins, rosin modified resins, terpene resins, polyester resins, polyamide resins, and epoxy resins. , Vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, and ethylene vinyl acetate resin. These resins may be used alone or in combination of two or more. Among these, it is one kind selected from the group consisting of urethane-based resins and (meth) acrylic-based resins because it has a high degree of design freedom and can easily adjust the elastic modulus to a range of 400 MPa to 1000 MPa. Or it is preferable that it is 2 or more types, and it is more preferable that it is a urethane type resin.

  The urethane resin is a resin having a urethane bond in the molecule. From the viewpoint of the storage stability of the ink, and the viewpoint of improving the reactivity with the pretreatment agent described later when the urethane-based resin contains a polyvalent metal compound, a carboxy group, a sulfo group, a hydroxy group, etc. An anionic urethane-based resin having an anionic functional group is preferable.

  The urethane-based resin is preferably a urethane-based resin having an alicyclic structure from the viewpoint of more reliably achieving the effects of the present invention. In order to obtain a urethane-based resin having an alicyclic structure, for example, a polyol compound containing a polycarbonate polyol having an alicyclic structure described later may be used as a raw material for the urethane-based resin.

  Examples of the urethane resin include, in addition to the urethane bond, a polyether type urethane resin having an ether bond in the main chain, a polyester type urethane resin having an ester bond in the main chain, and a polycarbonate type urethane resin having a carbonate bond in the main chain. . These urethane resins can be used in combination of multiple types. Among these, it is more preferable to use a polyether type urethane resin or a polycarbonate type urethane resin in terms of suppressing the generation of aggregates at a high level.

  (Meth) acrylic resin means a resin having a (meth) acrylic skeleton. Although it does not specifically limit as (meth) acrylic-type resin, For example, the polymer of (meth) acrylic-type monomers, such as (meth) acrylic acid and (meth) acrylic acid ester, (meth) acrylic-type single-piece | units A copolymer of a monomer and another monomer may be mentioned. Examples of the other monomer include vinyl monomers such as styrene. In the present specification, “(meth) acryl” is a concept including both “methacryl” and “acryl”.

  In order to obtain a resin having an elastic modulus of 400 MPa or more and 1000 MPa or less, for example, a prepolymer obtained by reacting a polyisocyanate compound, a polyol compound containing a polycarbonate polyol having an alicyclic structure, and an acidic group-containing polyol compound is used. It is preferable to prepare and react the prepolymer with a compound having two or more active hydrogen atoms in the molecule, which is reactive with the isocyanato group of the prepolymer. Examples of the compound having two or more active hydrogen atoms in the molecule include polyamine compounds containing two or more primary or secondary amino groups in one molecule, and polyol compounds.

  The acid value of the resin contained in the resin particles is preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, and further preferably 40 mgKOH / g or less. When the acid value is in such a numerical range, the generation of aggregates tends to be further suppressed. An acid value is measured by the method as described in the Example mentioned later.

  The average particle diameter of the resin particles is preferably 10 nm or more and 200 nm or less, more preferably 30 nm or more and 150 nm or less, and further preferably 50 nm or more and 100 nm or less. Thus, when the average particle diameter of the resin particles is 10 nm or more and 200 nm or less, it is excellent in ejection stability due to the suppression of the resin particles adhering to the nozzle.

  The average particle diameter in this specification is based on volume unless otherwise specified. As a measuring method, for example, it can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. Examples of the particle size distribution measuring device include a particle size distribution meter (for example, Microtrac UPA manufactured by Nikkiso Co., Ltd.) having a dynamic light scattering method as a measurement principle.

  The content of resin particles in the ink composition (in terms of solid content) is preferably 3.0% by mass or more and 55% by mass or less, and more preferably 5.0% by mass or more and 50% by mass or less with respect to the total amount (100% by mass) of the ink composition. More preferably, it is 10 mass% or more and 45 mass% or less. When the content of the resin particles is 10% by mass or more, the friction fastness and adhesion tend to be more excellent. Moreover, when the content of the resin particles is 55% by mass or less, the ejection stability tends to be more excellent.

<Softener>
The ink composition preferably further contains a softening agent from the viewpoint of obtaining a printed material having a better texture and texture. The softening agent is not particularly limited as long as it can impart flexibility to the obtained recorded matter, but a silicone compound is preferable. Here, the silicone compound means a polymer having a siloxane unit as a repeating unit, more specifically, a polymer in which an inorganic siloxane bond and an organic functional group such as a methyl group coexist in the same molecule. . The silicone compound is preferably an emulsion type silicone compound, which is a silicone-based water-dispersible resin, from the viewpoint of more effectively and reliably exhibiting the above-described effects of the softening agent.

  The molecular structure of the emulsion type silicone compound may be linear or branched or crosslinked. Further, the emulsion type silicone compound may be modified. In this case, the silicone compound is modified with one or more organic functional groups excluding a methyl group.

  Examples of organic functional groups include, but are not limited to, aromatic ring groups such as alkyl groups, phenyl groups, methylphenyl groups, and diphenyl groups, polyether groups, carboxyl groups, epoxy groups, and amino groups.

  Specific examples of the emulsion type silicone compound include, but are not limited to, for example, dimethyl silicone emulsion, methylphenyl silicone emulsion, amino-modified silicone emulsion, epoxy-modified silicone emulsion, polyether-modified silicone emulsion, alkyl-modified silicone emulsion, higher fatty acid. Modified silicone emulsion, methyl hydrogen silicone emulsion, fluorine modified silicone emulsion, carboxy modified silicone emulsion, polyglycerol modified silicone emulsion, carbinol modified silicone emulsion, epoxy polyether modified silicone emulsion, alkyl polyether modified silicone emulsion, and reactive silicone Emulsion listed It is.

  Among these, a group consisting of a dimethyl silicone emulsion, an epoxy-modified silicone emulsion, an amino-modified silicone emulsion, and a reactive silicone emulsion because of excellent compatibility in the ink composition and better flexibility and texture. One or more selected from the above are preferred. Hereinafter, these emulsion type silicone compounds will be described in detail, but the description of “emulsion” may be omitted in some cases.

First, the dimethyl silicone emulsion is preferable because the dynamic friction coefficient of the fabric can be further reduced. Among them, dimethyl silicone having a high degree of polymerization or kinematic viscosity is preferable. Specifically, the kinematic viscosity is preferably 1000 mm ² / s or more, and more preferably 10,000 mm ² / s or more. Here, the kinematic viscosity is a kinematic viscosity temperature measured at 25 ° C. Increasing the degree of polymerization increases the viscosity accordingly. Therefore, dimethyl silicone having a high viscosity is suitable for reducing the dynamic friction coefficient.

  Examples of such dimethyl silicone include, but are not limited to, for example, KF96A-2cs, 5cs, 6cs, 10cs, 20cs, 30cs, 50cs, 100cs, 200cs, 300cs, 350cs, 350cs, 500cs, KF-96-1000cs, 3000 cs, KF-96A-5000 cs, KF-96H-6000 cs, 10,000 cs, 120,000 cs, 30,000 cs, 50,000 cs, 60,000 cs, 100,000 cs, 300,000 cs, 500,000 cs, 1 million cs cs, and Polon MF-7, MF-17, and MF-32 (above, trade names manufactured by Shin-Etsu Chemical Co., Ltd.).

Moreover, said epoxy-modified silicone emulsion is suitable for obtaining a liquid softening agent composition capable of imparting fabric flexibility. Epoxy-modified silicones can also have a low coefficient of dynamic friction when the degree of polymerization or viscosity is increased. Specifically, those having a kinematic viscosity of 5000 mm ² / s or more are preferable.

  Examples of such epoxy-modified silicone include, but are not limited to, Polon MF-11C, MF-18T, and MF-24 (above, trade names manufactured by Shin-Etsu Chemical Co., Ltd.).

  The amino-modified silicone is preferable because it is excellent in the flexibility of the fabric and the texture of the printed material. Examples of the amino-modified silicone include, but are not limited to, Polon MF-14 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

  The reactive silicone emulsion is preferable because the strength of the coating film is increased and the printed product is excellent in abrasion resistance and washing fastness. Specific examples of the reactive silicone emulsion include, but are not limited to, addition reaction type, peroxide curable type, and photocurable type silicone emulsion. Examples of the commercially available products include TSR1500, TSR1510, TSR1511, TSR1515, TSR1520, YR3286, YR3340, PSA6574, TPR6500, TPR6501, TPR6600, TPR6702, TPR6604, TPR6700, TPR6701, TPR6707, TPR6767, TPR6767, TPR6767, TPR6767, TPR6767, TPR6767 , UV9300, UV9315, UV9425, UV9430, XS56-A2775, XS56-A2982, XS56-A3075, XS56-A3969, XS56-A5730, XS56-A8012, XS56-B1794, SL6100, SM3000, SM3030, SM3200, YSR3022 Recone trade name), KM-2002L-1 (Shin-Etsu Chemical Co., Ltd. trade name) and the like.

  The content of the softening agent is preferably 0.1% by mass or more and 3.0% by mass with respect to the total amount (100% by mass) of the ink composition. When the content is 0.1% by mass or more, the friction fastness is more excellent, and the storage stability of the ink composition and the flexibility of the printed matter tend to be better. On the other hand, when the content is 3.0% by mass or less, the viscosity of the ink composition can be effectively reduced, and the storage stability of the ink composition tends to be better. .

<Surfactant>
The ink composition preferably further contains a surfactant from the viewpoint of glossiness. The surfactant is not particularly limited, and examples thereof include acetylene glycol surfactants, fluorine surfactants, and silicone surfactants.

  The acetylene glycol surfactant is not particularly limited, but 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne- One selected from alkylene oxide adducts of 4,7-diol and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol The above is preferable. Although it does not specifically limit as a commercial item of an acetylene glycol type surfactant, For example, E series (A product made by Air Products Japan (Inc)) (Surfinol 104, etc.), such as Olfine 104 series and Olfine E1010, 465, 61, DF110D (trade name manufactured by Nissin Chemical Industry CO., Ltd.). One acetylene glycol surfactant may be used alone, or two or more acetylene glycol surfactants may be used in combination.

  Although it does not specifically limit as a fluorine-type surfactant, For example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, and A perfluoroalkylamine oxide compound is mentioned. Although it does not specifically limit as a commercial item of a fluorochemical surfactant, For example, S-144, S-145 (above brand name, Asahi Glass Co., Ltd. product); FC-170C, FC-430, Fluorard-FC4430 (above product) Name, manufactured by Sumitomo 3M Limited); FSO, FSO-100, FSN, FSN-100, FS-300 (above trade name, manufactured by Dupont); FT-250, 251 (above trade name, manufactured by Neos Co., Ltd.) Can be mentioned. A fluorine-type surfactant may be used individually by 1 type, and may use 2 or more types together.

  Although it does not specifically limit as a silicone type surfactant, For example, a polysiloxane type compound and a polyether modified organosiloxane are mentioned. Although it does not specifically limit as a commercial item of a silicone type surfactant, Specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK -348, BYK-349 (above trade name, manufactured by Big Chemie), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF- 642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. A silicone type surfactant may be used individually by 1 type and may use 2 or more types together.

  The surfactant content is preferably 0.05% by mass to 2.5% by mass and more preferably 0.05% by mass to 1.5% by mass with respect to the total amount (100% by mass) of the ink composition. It is below mass%. When the content of the surfactant is within the above range, the wettability of the ink composition attached to the recording medium tends to be further improved.

  The ink composition, as other components, affects wax, dissolution aids, viscosity modifiers, pH adjusters such as potassium hydroxide, antioxidants, fungicides / preservatives, antifungal agents, corrosion inhibitors, and dispersion. Various additives such as a chelating agent (for example, sodium ethylenediaminetetraacetate) for capturing a metal ion that gives a carbon atom can be appropriately contained.

  The ink composition of the present embodiment is preferably used in a textile printing method described later.

〔Recording method〕
The recording method of the present embodiment includes a step (recording step) of recording the above-described ink composition of the present embodiment on a recording medium. The recording method of the present embodiment may be a textile printing method in which the recording medium includes a fabric. FIG. 1 is a flowchart showing an example of the textile printing method of the present embodiment. As shown in FIG. 1, the textile printing method of this embodiment may further include the following heating step and cleaning step.

  The above textile printing method may be an ink jet textile printing method in which the ink composition is loaded into an ink jet apparatus and used. The ink jet device is not particularly limited, and examples thereof include a drop-on-demand ink jet device. This drop-on-demand ink jet apparatus includes an apparatus that employs an ink jet printing method using a piezoelectric element disposed on a head, and an ink jet that uses thermal energy from a heater of a heating resistance element disposed on the head. There are apparatuses that employ a printing method, and any of these inkjet printing methods may be used. Hereafter, each process which the inkjet textile printing method has is demonstrated in detail.

[Recording process]
The recording step of the present embodiment is a step of recording an ink composition described later on a recording medium. When the ink jet method is used, the ink composition is ejected by the ink jet method toward the surface (image forming region) of the cloth that is the recording medium, and is attached to the recording medium to form an image. The ejection conditions may be determined as appropriate depending on the physical properties of the ejected ink composition.

[Heating process]
The textile printing method of this embodiment may further include a heating step of heating the recording medium to which the ink composition is adhered after the recording step. By having a heating process, a color material can be dye | stained more favorably to the fiber which comprises a fabric. Although it does not specifically limit as a heating method, For example, HT method (high temperature steaming method), HP method (high pressure steaming method), and a thermosol method are mentioned.

  In the heating step, the ink composition adhesion surface on the recording medium may or may not be subjected to pressure treatment. As a heating method in which the ink composition adhesion surface on the recording medium is not pressure-treated, oven drying (a method in which a press such as a conveyor oven or a batch oven is not performed) can be given. By having such a heating step, recorded product productivity is further improved. Further, the heating method for performing the pressure treatment on the ink composition adhesion surface on the recording medium is not particularly limited, and examples thereof include heat press and wet on dry. “Pressurization” refers to applying pressure by bringing an individual into contact with a recording medium.

  The temperature during the heat treatment is preferably 80 ° C. or higher and 150 ° C. or lower, more preferably 90 ° C. or higher and 110 ° C. or lower. When the temperature during the heat treatment is in the above range, the color material tends to be more satisfactorily dyed on the fibers constituting the fabric.

[Washing process]
The textile printing method of this embodiment may further include a cleaning step of cleaning the recording medium to which the ink composition is adhered after the heating step. The washing step can effectively remove the pigment not dyed on the fiber. The cleaning process can be performed using, for example, water, and a soaping process may be performed as necessary. The soaping treatment method is not particularly limited, and examples thereof include a method of washing off unfixed pigment with a hot soap solution or the like.

  In this way, it is possible to obtain a recorded matter such as a printed matter in which an image derived from the ink composition is formed on a recording medium including a fabric.

<Recording medium>
The recording medium of the present embodiment is not particularly limited, and examples thereof include an absorptive recording medium, a low absorptive recording medium, a non-absorbing recording medium, and a fabric, including a fabric (cloth) Including itself).

Here, the “low-absorbing recording medium” or “non-absorbing recording medium” refers to a recording medium having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec in the Bristow method. . This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

  Further, the non-absorbent recording medium or the low-absorbing recording medium can be classified by the wettability of the recording surface with respect to water. Specifically, a 0.5 μL water droplet is dropped on the recording surface of the recording medium, and the contact angle reduction rate (comparison of the contact angle at 0.5 milliseconds after the landing and the contact angle at 5 seconds) is measured. Can be used to characterize the recording medium. More specifically, as a property of the recording medium, the non-absorbing property of the “non-absorbing recording medium” indicates that the above-described reduction rate is less than 1%, and the low absorption of the “low-absorbing recording medium”. The property indicates that the decrease rate is 1% or more and less than 5%. Moreover, absorptivity means that said reduction rate is 5% or more. In addition, a contact angle can be measured using portable contact angle meter PCA-1 (made by Kyowa Interface Science Co., Ltd.) etc.

  The absorbent recording medium is not particularly limited. For example, plain paper such as electrophotographic paper having high penetrability of the ink composition, inkjet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl chloride). Art paper used for general offset printing in which the ink composition has a relatively low permeability from an alcohol (PVA) or polyvinyl pyrrolidone (PVP) or other hydrophilic polymer such as an ink-absorbing layer. , Coated paper and cast paper.

  Although it does not specifically limit as a low absorptive recording medium, For example, the coated paper by which the coating layer for accepting oil-based ink was provided in the surface is mentioned. The coated paper is not particularly limited, and examples thereof include printing paper such as art paper, coated paper, and matte paper.

  The non-absorbable recording medium is not particularly limited. For example, a plastic film that does not have an ink absorbing layer, a substrate such as paper coated with plastic, or a plastic film bonded thereto Etc. Examples of the plastic here include polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene.

  In addition to the above recording medium, a non-ink-absorbing or low-absorbing recording medium such as a plate made of a metal such as iron, silver, copper, or aluminum, or glass can also be used.

  Examples of the fabric include, but are not limited to, natural fibers and synthetic fibers such as silk, cotton, wool, nylon, polyester, and rayon. The fabric may be composed of one type of fiber or a mixture of two or more types of fibers. Of these, the effect of the present embodiment tends to be more easily obtained by using a mixture of fibers having different permeability. As the fabric, the above-described fibers may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric.

  The recording medium containing the cloth may be the cloth itself, but it is preferable that the cloth is pretreated with a pretreatment liquid containing resin particles. By pre-treating the fabric, there is a tendency to obtain a printed product having more excellent friction fastness. The cloth pretreatment with the pretreatment liquid containing resin particles may be a conventionally known method.

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited in any way by the following examples.

[Average particle size]
The average particle diameter φ (nm) of the aqueous urethane resin dispersion obtained below was measured by “Microtrac UPA” (Nikkiso Co., Ltd.).

[Acid value]
The aqueous urethane resin dispersion obtained below was measured using a potentiometric automatic titration device “AT610” manufactured by Kyoto Electronics Manufacturing Co., Ltd., and the numerical values were applied to the following equations. The acid value was calculated.
Acid value (mgKOH / g) = (EP1-BL1) × FA1 × C1 × K1 / SIZE
In the above formula, EP1 is a titration amount (unit: mL) of a KOH aqueous solution (titrant), BL1 is a blank value (0.0 mL), FA1 is a factor (1.00) of the titrant, and C1 is a concentration converted value ( 5.611 mg / mL) (0.1 mo1 / L KOH equivalent to 1 mL of potassium hydroxide), K1 is a coefficient (1), and SIZE is a sampling amount (unit: g).

[Elastic modulus]
About the urethane resin film obtained below, according to JIS-K7311, the elasticity modulus was measured on conditions of 23 degreeC and 50% RH using the tensile tester (made by Orientec; Tensilon UCT-5T).

[100% modulus]
About the urethane resin film obtained below, using a tensile testing machine (Orientec; Tensilon UCT-5T), the tensile load when the test piece is 100% elongated under the conditions of 23 ° C. and 50% RH The 100% modulus was determined by the following equation.
100% modulus (MPa) = F _100% / A
However, F _100% indicates the tensile load (N) at 100% elongation, and A indicates the cross-sectional area (mm ² ) of the test piece.

[Production Example 1] Resin dispersions (1-1), (1-2), (1-3), resin films (1-1), (1-2), (1-3)
In a reaction vessel in which a stirrer, a reflux condenser and a thermometer were inserted, ETERNCOLLUM UM90 (3/1) (Ube Industries' polycarbonate diol; number average molecular weight 916; hydroxyl value 122.5 mgKOH / g; 1,4-cyclohexanedimethanol: 150 g of polycarbonate diol obtained by reacting a polyol mixture of a molar ratio of 1,6-hexanediol = 3: 1 and a carbonate ester), 22 g of 2,2-dimethylolpropionic acid (DMPA) and 134 of methyl ethyl ketone (MEK) .7 g was charged under a nitrogen stream. Thereafter, it was heated to 60 ° C., and it was confirmed that DMPA was dissolved. Thereto, 144.5 g of 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.26 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C., followed by urethanization reaction over 5 hours. A prepolymer was obtained. The reaction mixture was cooled to 80 ° C., 434 g was extracted from the mixture in which 14.9 g of triethylamine was added and mixed, and added to a mixed solution of 540 g of water and 1.5 g of triethylamine under strong stirring. Next, 150 g of ice was added thereto, and 62.6 g of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction. The product was heated at room temperature to 50 ° C. under reduced pressure for 3 hours to remove MEK to obtain a resin dispersion (1-1). Further, in the above production conditions, the same operation was performed except that the amount of 2,2-dimethylolpropionic acid (DMPA) charged was increased from 22 g to 32.1 g and 44.8 g, respectively. Resin dispersion (1-2) (acid value: 41 mgKOH / g) and resin dispersion (1-3) (acid value: 55 mgKOH / g) were obtained, respectively.

  Resin dispersions (1-1), (1-2), and (1-3) were each coated on a glass plate and dried at 120 ° C. for 3 hours. The film thicknesses of the obtained resin films (1-1), (1-2), and (1-3) were 0.13 mm, respectively. Table 1 shows the results of the elastic modulus and 100% modulus in the tensile tests of the resin films (1-1), (1-2), and (1-3).

[Production Example 2] Resin dispersion (2), resin film (2)
In the same reaction vessel as in Production Example 1, ETERNACOLL UM90 (3/1) (Ube Industries polycarbonate diol; number average molecular weight 916; hydroxyl value 122.5 mgKOH / g; 1,4-cyclohexanedimethanol: 1,6-hexane 150 g of a polycarbonate diol obtained by reacting a polyol mixture having a molar ratio of diol = 3: 1 and a carbonate ester), 7.46 g of 1,4-butanediol, and 39. 2,2-dimethylolpropionic acid (DMPA). 9 g and 186 g of methyl ethyl ketone (MEK) were charged under a nitrogen stream. Thereafter, it was heated to 60 ° C., and it was confirmed that DMPA was dissolved. Thereto, 239 g of 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.35 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C. to carry out a urethanization reaction over 5 hours. Got. The reaction mixture was cooled to 80 ° C., 582 g was extracted from the mixture in which 26.4 g of triethylamine was added and mixed, and added to a mixed solution of 726 g of water and 2.56 g of triethylamine under strong stirring. Next, 204 g of ice was added thereto, and 103 g of a 35 mass% 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction. The product was heated at room temperature to 50 ° C. under reduced pressure for 3 hours to remove MEK to obtain a resin dispersion (2).

  In the same manner as in Production Example 1, a resin film having a thickness of 0.13 mm was produced from the resin dispersion (2). Table 1 shows the results of the elastic modulus and 100% modulus in the tensile test of the obtained resin film (2).

[Production Example 3] Resin dispersion (3), resin film (3)
In the same reaction vessel as in Production Example 1, ETERNACOLL UM90 (1/3) (Ube Industries' polycarbonate diol; number average molecular weight 894; hydroxyl value 125.5 mgKOH / g; 1,4-cyclohexanedimethanol: 1,6-hexane 150 g of a polycarbonate diol obtained by reacting a polyol mixture having a molar ratio of diol = 1: 3 and a carbonate ester), 7.53 g of 1,4-butanediol, and 2,2-dimethylolpropionic acid (DMPA). 3 g and 188 g of methyl ethyl ketone (MEK) were charged under a nitrogen stream. Thereafter, it was heated to 60 ° C., and it was confirmed that DMPA was dissolved. Then, 245g of 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.35g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C to carry out urethanization reaction for 5 hours to obtain a urethane prepolymer. Got. The reaction mixture was cooled to 80 ° C., 606 g was extracted from the mixture in which 26.7 g of triethylamine was added and mixed, and added to a mixed solution of 776 g of water and 2.92 g of triethylamine under strong stirring. Next, 163 g of ice was added, and 108 g of a 35 mass% 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction. The product was heated at room temperature to 50 ° C. under reduced pressure for 3 hours to remove MEK to obtain a resin dispersion (3).

  In the same manner as in Production Example 1, a resin film having a thickness of 0.13 mm was produced from the resin dispersion (3). Table 1 shows the results of the elastic modulus and 100% modulus in the tensile test of the obtained resin film (3).

[Production Example 4] Resin dispersion (4), resin film (4)
It is obtained by reacting ETERRNACOLL UH-100 (Ube Industries polycarbonate diol; number average molecular weight 1004; hydroxyl value 111.8 mgKOH / g; 1,6-hexanediol and carbonate ester in the same reaction vessel as in Production Example 1. Polycarbonate diol) 80.1 g, 1,4-butanediol 0.96 g, 2,2-dimethylolpropionic acid (DMPA) 12.1 g and methyl ethyl ketone (MEK) 73.6 g were charged under a nitrogen stream. Thereafter, it was heated to 60 ° C., and it was confirmed that DMPA was dissolved. Thereto, 80.8 g of 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.23 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C., followed by urethanization reaction over 5 hours. A prepolymer was obtained. The reaction mixture was cooled to 80 ° C., and 236 g was extracted from the mixture in which 9.10 g of triethylamine was added and mixed, and added to 300 g of water under strong stirring. Next, 84.4 g of ice was added thereto, and 38.5 g of a 35 mass% 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction. The product was heated at room temperature to 50 ° C. under reduced pressure for 3 hours to remove MEK to obtain a resin dispersion (4).

  In the same manner as in Production Example 1, a resin film having a thickness of 0.13 mm was produced from the resin dispersion (4). Table 1 shows the results of the elastic modulus and 100% modulus in the tensile test of the obtained resin film (4).

[Production Example 5] Resin dispersion (5), resin film (5)
In the same reaction vessel as in Production Example 1, ETERNACOLL UM90 (1/3) (Ube Industries' polycarbonate diol; number average molecular weight 894; hydroxyl value 125.5 mgKOH / g; 1,4-cyclohexanedimethanol: 1,6-hexane Polycarbonate diol obtained by reacting a polyol mixture with a molar ratio of diol = 1: 3 and a carbonate ester) 79.6 g, 2,2-dimethylolpropionic acid (DMPA) 9.60 g and methyl ethyl ketone (MEK) 68. 5 g was charged under a nitrogen stream. Thereafter, it was heated to 60 ° C., and it was confirmed that DMPA was dissolved. Thereto, 70.9 g of 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.20 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C. to carry out a urethanization reaction over 5 hours. A prepolymer was obtained. The reaction mixture was cooled to 80 ° C., 211 g was extracted from the mixture in which 7.21 g of triethylamine was added and mixed, and added to 277 g of water under strong stirring. Next, 62.2 g of ice was added thereto, and 30.7 g of a 35 mass% 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction. The product was heated at room temperature to 50 ° C. under reduced pressure for 3 hours to remove MEK to obtain a resin dispersion (5).

  In the same manner as in Production Example 1, a resin film having a thickness of 0.13 mm was produced from the resin dispersion (5). Table 1 shows the results of the elastic modulus and 100% modulus in the tensile test of the obtained resin film (5).

[Material for ink composition]
The main materials for the ink composition used in the preparation of the following recorded matter are as follows.
[Color material]
Magenta pigment (CI Pigment Red 122)
[Resin particles]
Resin dispersions (1-1), (1-2), (1-3), (2) to (5)
〔Organic solvent〕
Glycerin Triethylene glycol 2-Pyrrolidone Triethylene glycol monobutyl ether [Surfactant]
BYK-348 (silicone surfactant, trade name manufactured by BYK)
[PH adjuster]
Potassium hydroxide (mold and antiseptic)
Proxel XL2 (trade name, manufactured by Arch Chemicals)
〔Softener〕
Polon-MF-14 (Amino-modified silicone emulsion, trade name manufactured by Shin-Etsu Chemical Co., Ltd.)

[Preparation of ink composition]
Each material was mixed with the composition shown in Table 2 and Table 3 below, and stirred sufficiently to obtain an ink composition. In Tables 2 and 3 below, the unit of numerical values is mass%, the numerical values are solid content concentrations, and the total is 100.0 mass%.

[Production of printed matter]
The ink compositions 14 to 27 prepared above were adhered to the fabric by an inkjet method using an inkjet printer (product name “PX-G930” manufactured by Seiko Epson Corporation). As recording conditions, the recording resolution was 1440 dpi × 1440 dpi, the recording range was A4 size, and four layers of solid pattern images were overcoated. Inkjet printing was performed in this manner. Here, the “solid pattern image” means an image in which dots are recorded for all of the pixels that are the minimum recording unit area defined by the recording resolution.

  Thereafter, heat treatment was performed at 160 ° C. for 1 minute using a heat press, and the ink composition was fixed on the recording medium. In this way, a printed material having an image formed on the recording medium (ink printed) was produced.

(Discharge stability)
After the above [Preparation of printed matter], nozzle clogging was confirmed, and ejection stability was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5.
(Evaluation criteria)
A: There was no clogging or clogging disappeared by performing head cleaning once.
B: Clogging did not disappear even after one head cleaning, but disappeared by two or three head cleanings.
C: The clogging did not disappear even after performing the head cleaning three times.

[Clogging recovery]
Prepare an inkjet printer (product name “PX-G930”, manufactured by Seiko Epson Corporation), fill the cartridge of the printer with the ink composition, and leave the cartridge cap open at room temperature for one month. did. Thereafter, the 360 nozzles of the cartridge were subjected to head cleaning three times, and the clogging recoverability was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5.
(Evaluation criteria)
A: The number of defective nozzles and the number of nozzles whose ejection direction is shifted are 0 with respect to the total number of nozzles.
B: The number of nozzles with defective ejection and the number of nozzles with different ejection directions are 1 to 2 with respect to the total number of nozzles.
C: The number of defective nozzles and the number of nozzles whose ejection direction is shifted are 3 to 5 or more with respect to the total number of nozzles.
D: The number of nozzles with defective ejection and the number of nozzles with different ejection directions are 6 to 10 or more with respect to the total number of nozzles.
E: The number of nozzles with defective ejection and the number of nozzles with different ejection directions are 11 or more with respect to the total number of nozzles.

[Texture]
The texture was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5.
A: The touch of the printed material is almost the same as that of the original fabric.
B: The touch of the printed material feels somewhat harder than the original fabric.
C: The touch of the printed material became harder than the original fabric.
D: The touch of the printed material was clearly harder than the original fabric.

[Filter aggregate]
The ink composition obtained above was connected to an ink jet printer (PX-G930, manufactured by Seiko Epson Corporation), and 500 mL each was filled in the ink containing container. Next, the ink storage container was brought into a ready-to-use posture, and then left for 2 weeks under conditions of a temperature of 40 ° C., a relative humidity of 20% RH, and an open air system. Two weeks later, 500 mL of ink in the ink storage container is supplied from the ink storage container to the recording head through the sub tank in the printer, and is discharged from the recording head to be provided in an ink supply pipe that connects the ink storage container and the sub tank. The clogged state of the filter (material SUS, mesh pore diameter 3.5 μm) was confirmed. The clogged state of the filter was evaluated by checking the surface of the filter using a digital microscope VHX-900 (manufactured by Keyence Corporation) and calculating the clogged area (%) with respect to the area of the filter. Since the amount of liquid passing was 3% of the expected usage amount of the ink jet printer, the clogging area was calculated by multiplying the clogging amount by 30 and evaluated according to the following criteria.
A: Filter clogging area is 5.0% or less B: Filter clogging area is more than 5.0% and 10% or less C: Filter clogging area is more than 10% and 15% or less D: Filter clogging area More than 15% and less than 20% E: The clogging area of the filter is more than 20%

[Friction fastness]
For each printed matter, normal washing (washing conditions: washing in normal mode, dehydration, drying) was performed 5 times in a home washing machine, and the image density (initial value, OD value) before washing of each recorded matter. ) And the image density after washing (OD value) were measured using a Macbeth densitometer (manufactured by Macbeth, “TD-931”), and the friction fastness was evaluated according to the following evaluation criteria. The results are shown in Tables 4 and 5.
(Evaluation criteria)
A: Image density after washing is 90% or more before washing B: Image density after washing is 80% or more and less than 90% before washing C: Image density after washing is 70% or more and 80% before washing Less than D: Image density after washing is 60% or more and less than 70% before washing E: Image density after washing is less than 60% before washing

DESCRIPTION OF SYMBOLS 11 ... Inkjet recording device, 12 ... Wheel, 13 ... Leg part, 14 ... Apparatus main body, 15 ... Feeding part, 16 ... Housing | casing part, 17 ... Insertion port, 18 ... Discharge port, 19 ... Medium receiving unit, 20 ... Operation panel 21, 200 ... Ink container, 22 ... Ink container unit, 23 ... Frame member, 24, 300 ... Recording head, 25 ... Carriage, 202 ... Plug member, 204 ... Ink inlet, 211 ... Container body, 212 DESCRIPTION OF SYMBOLS ... Air inlet, 214 ... Ink storage chamber, 216 ... Ink lead-out part, 217 ... Air release port, 218 ... Air introduction port, 230 ... Air storage chamber, 250 ... Ink chamber communication path, 251 ... Air chamber side opening, 270C1 ... first wall, 270C2 ... second wall, 270C3 ... bottom wall, 400 ... ink supply path, R ... roll paper, S ... paper, sf ... horizontal plane, G ... bubble

Claims (8)

An ink-jet ink composition comprising a coloring material, water, an organic solvent, and resin particles,
The resin particles include a resin having an elastic modulus of 400 MPa to 1000 MPa,
The inkjet ink composition whose total content of the pyrrolidones and glycol monoethers in an organic solvent is 1.5 mass% or less with respect to the total amount of the said inkjet ink composition.   The inkjet ink composition according to claim 1, wherein the resin particles are particles containing one or more selected from the group consisting of urethane resins and (meth) acrylic resins.   The inkjet ink composition according to claim 1, further comprising a softening agent.   The ink-jet ink composition according to any one of claims 1 to 3, wherein the acid value of the resin particles is 60 mgKOH / g or less.   The inkjet resin composition according to claim 1, wherein the resin particles are self-emulsifying resin particles.   The inkjet ink composition according to any one of claims 1 to 5, wherein an average particle diameter of the resin particles is 10 nm or more and 200 nm or less.   The inkjet ink composition according to any one of claims 1 to 6, which is used in a method of recording the ink composition on a recording medium containing a fabric.   A printing method comprising a step of recording the inkjet ink composition according to any one of claims 1 to 7 on a recording medium containing a fabric.

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