JP2018002833A - Inkjet ink composition, and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet ink composition that contains a resin particle and has, at the same time, excellent discharge stability, and also produces a recorded matter with excellent solvent resistance.SOLUTION: An inkjet ink composition contains a colorant, water, an organic solvent, and a resin particle containing a fluorine-containing resin. The resin particle has the fluorine-containing resin exposed on at least a part of the surface of the resin particle.SELECTED DRAWING: None

Description

  The present invention relates to an inkjet ink composition and a recording 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, Patent Document 1 discloses that an ink jet or ink mist recording method in which fine droplet ink or mist ink is ejected from a recording head, and the ink is attached to plain paper to perform printing is performed on the plain paper. Ink jet or ink mist for the purpose of providing an ink for image recording excellent in ejection stability and storage stability that does not cause bleeding, has good drying and fixing properties, has no tailing, and does not clog. In the image recording ink used in the recording method, at least water, 0.5 to 10% by weight of a dye and / or pigment, and polymer fine particles having a two-layer structure having an average particle size of 0.1 μm or less are used as an aqueous emulsion solution. An image recording ink containing -40% by weight is disclosed.

Japanese Patent Laid-Open No. 3-160069

  However, when the ink disclosed in Patent Document 1 is used, there is room for improvement although excellent ejection stability was obtained at the time when the Patent Document was issued. Specifically, a conventional ink composition containing water contains resin particles for fixing a coloring material such as a pigment to a recording medium. However, when the ink composition contains an organic solvent, the organic solvent welds or fuses a part of the resin particles, and the resin particles adhere to the nozzle surface of the discharge nozzle that discharges the ink composition. Due to the sticking, excellent discharge stability cannot be obtained at a high level. On the other hand, when the ink composition does not contain an organic solvent, although excellent ejection stability can be obtained, the fixability of the resin particles after adhering to the recording medium is suppressed, The recorded matter obtained is not excellent in solvent resistance.

  SUMMARY An advantage of some aspects of the invention is that it provides an ink composition that includes resin particles and has excellent ejection stability.

  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 containing a fluorine-containing resin, and the resin particles are at least on the surface of the resin particles. By using an ink composition in which the fluororesin is partly exposed, it was found that the discharge stability was excellent and the solvent resistance of the resulting recorded matter was excellent, and the present invention was completed.

  That is, the present invention includes a color material, water, an organic solvent, and resin particles containing a fluorine-containing resin, and the resin particles are exposed on at least a part of the surface of the resin particles. The ink composition. The reason why such an 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 composition according to the present invention mainly suppresses the fusion of the resin particles on the nozzle surface of the discharge nozzle by exposing the fluororesin to at least a part of the surface of the resin particles. As a result, the discharge stability is excellent. In addition, the ink composition according to the present invention mainly contains an organic solvent, so that the resin in the resin particles landed on the recording medium is fused by impact of impact or heating. The surface of the resin is protected by the resin, and the solvent resistance is excellent.

  In the ink composition according to the present invention, the fluorine-containing resin may be polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene. Preferably, it is one or more selected from the group consisting of a copolymer, polyvinylidene fluoride, and an ethylene / chlorotrifluoroethylene copolymer, and the resin particles include a core comprising a core resin and a shell resin. -It has a shell structure, and the shell resin preferably contains the fluorine-containing resin, and the thickness of the portion of the fluorine-containing resin contained in the shell resin is preferably 1.0 nm or more and 100 nm or less, The core resin preferably contains a urethane resin, and the resin particles The average particle diameter is preferably 10 nm or more and 400 nm or less, and the content of the resin particles is 1.0% by mass or more and 20% by mass or less in terms of solid content with respect to the total amount of the ink composition. Preferably, the color material is a pigment or a dye, and the content of the color material is preferably 0.3% by mass or more and 5.0% by mass or less based on the total amount of the ink composition. .

  Furthermore, the recording method according to the present invention includes a step of recording the ink composition on a recording medium to obtain a recorded material.

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 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 material” refers to an image formed by recording ink on a recording medium.

[Ink composition]
The ink composition of the present embodiment includes a coloring material, water, an organic solvent, and resin particles containing a fluorine-containing resin. Further, the fluororesin is exposed on at least a part of the surface of the resin particles. The reason why such an ink composition is excellent in ejection stability and the solvent resistance of the obtained recorded matter is considered as follows. However, the factor is not limited to this. That is, the ink composition of the present embodiment mainly suppresses the resin particles from being welded or fused on the nozzle surface of the discharge nozzle by exposing the fluororesin to at least a part of the surface of the resin particles. As a result, the discharge stability is excellent. In addition, the ink composition according to the present invention mainly contains an organic solvent, so that the resin in the resin particles landed on the recording medium is fused by impact of impact or heating. The surface of the resin is protected by the resin, and the solvent resistance is excellent.

<Color material>
The color material of this embodiment can contain a pigment or a dye.

  Although it does not specifically limit as a pigment, For example, the following are mentioned. A pigment is used individually by 1 type or in combination of 2 or more types.

  Carbon black used for the black ink is not particularly limited. I. Pigment black 7, no. 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, 254 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, 13: 5, 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.

  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.

  The color material preferably contains one or more pigments selected from the group consisting of self-dispersing pigments and resin-dispersed pigments. Thereby, the color material tends to be more excellent in glossiness due to the uniform dispersion in the recorded matter.

The self-dispersing pigment is a pigment having a hydrophilic group on its surface. As the hydrophilic group, -OM, -COOM, -CO -, - SO 3 M, -SO 2 M, -SO 2 NH 2, -RSO 2 M, -PO 3 HM, -PO 3 M 2, -SO 2 It is preferably at least one hydrophilic group selected from the group consisting of NHCOR, —NH ₃ , and —NR ₃ .

  In these chemical formulas, M represents a hydrogen atom, an alkali metal, ammonium, an optionally substituted phenyl group, or organic ammonium, and R represents an alkyl group having 1 to 12 carbon atoms or a substituted group. A naphthyl group which may have a group is represented. The above M and R are selected independently of each other.

  Specifically, the self-dispersing pigment is produced by subjecting the pigment to physical treatment and / or chemical treatment to bond (graft) the hydrophilic group to the surface of the pigment. Specific examples of the physical treatment include vacuum plasma treatment. Further, as the chemical treatment, specifically, a wet oxidation method in which oxidation is performed with an oxidizing agent in water, a method in which p-aminobenzoic acid is bonded to the pigment surface to bond a carboxyl group via a phenyl group, and the like can be mentioned. It is done.

  The resin-dispersed pigment is a pigment that can be dispersed in a liquid by a resin. The content of the resin with respect to the pigment can be expressed as the coverage of the resin coating the pigment. The resin coverage is preferably 1.0% to 50%, more preferably 1.0% to 10%, and still more preferably 1.0% to 5.0%. When the coverage is 1.0% or more, the dispersibility tends to be good. Further, when the coverage is 50% or less, the color developability tends to be further improved, and when it is 5.0% or less, the color developability tends to be even better. is there.

  70 mass% or more of the said resin is preferable in it being resin by copolymerization of (meth) acrylic acid and (meth) acrylic acid among the structural components. Thereby, it tends to be further excellent in the fixing property and glossiness of the ink. Further, at least one of alkyl (meth) acrylate (alkyl having 1 to 24 carbon atoms) and cyclic alkyl (meth) acrylate (cyclic alkyl having 3 to 24 carbon atoms) is polymerized from a monomer component of 70% by mass or more. More preferably. Specifically, as the monomer component, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) Pentyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, (meth) acrylic Dicyclopentanyl acid, dicyclopentenyl (meth) acrylate, ) Acrylate dicyclopentenyloxyethyl, and behenyl (meth) acrylate and the like. In addition, as other monomer components for polymerization, hydroxy (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, (meth) acrylic acid Examples thereof include urethane and (meth) acrylic acid epoxy.

  Although it does not specifically limit as dye, For example, the following are mentioned. A dye is used individually by 1 type or in combination of 2 or more types. The dye is preferably a sublimable dye. Here, the “sublimable dye” refers to a dye having a property of sublimating by heating.

  Although it does not specifically limit as black dye, For example, C.I. I. Disperse Black 1, 3, 10, and 24 are listed.

  Although it does not specifically limit as yellow dye, For example, C.I. I. Disperse Yellow 3, 4, 5, 7, 9, 13, 23, 24, 30, 33, 34, 42, 44, 49, 50, 51, 54, 56, 58, 60, 63, 64, 66, 68 71, 74, 76, 79, 82, 83, 85, 86, 88, 90, 91, 93, 98, 99, 100, 104, 108, 114, 116, 118, 119, 122, 124, 126, 135 140, 141, 149, 160, 162, 163, 164, 165, 179, 180, 182, 183, 184, 186, 192, 198, 199, 202, 204, 210, 211, 215, 216, 218, 224 227, 231 and 232. Although it does not specifically limit as an orange dye, For example, C.I. I. Disperse Orange 1, 3, 5, 7, 11, 13, 17, 20, 21, 25, 29, 30, 31, 32, 33, 37, 38, 42, 43, 44, 45, 46, 47, 48 49, 50, 53, 54, 55, 56, 57, 58, 59, 61, 66, 71, 73, 76, 78, 80, 89, 90, 91, 93, 96, 97, 119, 127, 130 139 and 142.

  Although it does not specifically limit as a red dye, For example, C.I. I. Disperse thread 1, 4, 5, 7, 11, 12, 13, 15, 17, 27, 43, 44, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 78, 81, 82, 86, 88, 90, 91, 92, 93, 96, 103, 105, 106, 107, 108, 110, 111, 113, 117, 118, 121, 122, 126, 127, 128, 131, 132, 134, 135, 137, 143, 145, 146, 151, 152, 153, 154, 157, 159, 164, 167, 169, 177, 179, 181, 183, 184, 185, 188, 189, 190, 191, 192, 200, 201, 202, 203, 205, 206, 207, 210, 221, 224, 225, 2 7,229,239,240,257,258,266,277,278,279,281,288,298,302,303,310,311,312,320,324, and 328, and the like. Although it does not specifically limit as violet dye, For example, C.I. I. Disperse violet 1, 4, 8, 23, 26, 27, 28, 31, 33, 35, 36, 38, 40, 43, 46, 48, 50, 51, 52, 56, 57, 59, 61, 63 , 69, and 77.

  Although it does not specifically limit as a blue dye, For example, C.I. I. Disperse Blue 3, 7, 9, 14, 16, 19, 20, 26, 27, 35, 43, 44, 54, 55, 56, 58, 60, 62, 64, 71, 72, 73, 75, 79 81, 82, 83, 87, 91, 93, 94, 95, 96, 102, 106, 108, 112, 113, 115, 118, 120, 122, 125, 128, 130, 134, 139, 141, 142 , 143, 146, 148, 149, 153, 154, 158, 165, 167, 171, 173, 174, 176, 181, 183, 185, 186, 187, 189, 197, 198, 200, 201, 205, 207 211, 214, 224, 225, 257, 259, 266, 267, 268, 270, 284, 285, 287, 288, 291, 293, 95,297,301,315,330,333,359, and 360, and the like.

  Moreover, it is although it does not specifically limit as dyes other than the above, For example, a green dye and a brown dye are mentioned. Although it does not specifically limit as a green dye, For example, C.I. I. Disperse Green 9 is an example. Although it does not specifically limit as brown dye, For example, C.I. I. Disperse Brown 1, 2, 4, 9, 13, 19 are listed.

  Examples of such a dye include a disperse dye having an anthraquinone skeleton that may have a substituent and a dye having an azo skeleton that may have a substituent. Among these, a dye having an anthraquinone skeleton which may have a substituent is preferable. When the dye is a dye having an anthraquinone skeleton, the wettability of the ink composition with respect to the recording apparatus such as the inner wall of the nozzle is further improved, and the ejection stability tends to be further improved. Although it does not specifically limit as a substituent, For example, a halogen group, a hydroxyl group, an amino group, a nitro group, and a carboxyl group are mentioned.

  In the ink composition, the content of the coloring material is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5% by mass or less with respect to the total amount (100% by mass) of the ink composition. It is 0.0 mass% or less, More preferably, it is 0.5 mass% or more and 3.0 mass% or less, More preferably, it is 1.0 mass% or more and 2.0 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>
Examples of the water in this embodiment include water from which ionic impurities are 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.
In the ink composition, the content of water is preferably 20% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 85% by mass with respect to the total amount (100% by mass) of the ink composition. Or less, and more preferably 50% by mass or more and 80% by mass or less.

<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. By including the organic solvent, the resin particles adhering to the recording medium are fixed on the surface of the recording medium, so that excellent friction fastness and texture are obtained along with excellent solvent resistance. Specifically, the conventional ink composition contains an organic solvent in addition to the resin particles, and when the ink composition is ejected onto the recording medium, the fixing of the resin particles on the surface of the recording medium is promoted. On the other hand, the organic solvent welds part of the resin particles, and the resin particles adhere to the nozzle surface of the discharge nozzle that discharges the ink composition. Stability may not be obtained. On the other hand, the ink composition of this embodiment has the fluororesin exposed on at least a part of the surface of the resin particles, so that the above-mentioned welding hardly occurs even if it contains an organic solvent, and the discharge nozzle It is inferred that the resin particles can be prevented from sticking to the nozzle surface (however, the factor is not limited to this).

  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. The organic solvent of this embodiment can be used by appropriately selecting various organic solvents from these organic solvents. Among these organic solvents, it is preferable to use a water-soluble organic solvent.

  The organic solvent preferably contains at least one of a cyclic nitrogen compound and an aprotic polar solvent. By containing a cyclic nitrogen compound or an aprotic polar solvent, the ink composition can shift the apparent glass transition temperature of the resin particles to a lower temperature side, and soften the core resin and shell resin at a lower temperature than the original. Therefore, the fixability of the ink composition to the recording medium tends to be improved. Thereby, particularly when the recording medium is made of polyvinyl chloride, the fixability of the ink composition to the recording medium can be improved.

  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.

  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.

  The alkyl polyol is not particularly limited. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol (1,2-propanediol), dipropylene glycol, 1,3-propylene glycol (1, 3-propanediol), 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-hexane A diol, 1,7-heptanediol, and It includes 8-octanediol.

  Although it does not specifically limit as glycol ether, For example, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t -Butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether , Propylene glycol mono-iso-propyl ether, propylene glycol Call mono -n- butyl ether, dipropylene glycol mono -n- butyl ether, dipropylene glycol mono -n- propyl ether, and dipropylene glycol monomethyl -iso- propyl ether and the like.

The organic solvent preferably contains at least one of an alkyl polyol and a glycol ether.
Moreover, it is also preferable to contain the organic solvent whose standard boiling point is 280 degreeC or more as an organic solvent. An example of such an organic solvent is glycerin.
More preferably, an organic solvent having a normal boiling point of 280 ° C. or higher and an organic solvent having a standard boiling point of less than 280 ° C. are used in combination. As a result, in the heating step after ink landing, welding is further promoted, adhesion to the recording medium is improved, and solvent resistance and friction fastness tend to be further improved.

  The content of the organic solvent is preferably 5.0% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less, with respect to the total amount (100% by mass) of the ink composition. Preferably they are 20 mass% or more and 40 mass% or less. When the content of the organic solvent is 60% by mass or less, the ejection stability and clogging recovery property of the ink composition attached to the recording medium tend to be further improved. Further, when the content of the organic solvent is 5.0% by mass or more, it tends to be more excellent in friction fastness and texture. That is, according to the ink composition of the present embodiment, even when the content of the organic solvent is relatively large (for example, 20% by mass or more), the resin particles are hardly welded, and the resin particles with respect to the nozzle surface of the discharge nozzle It is presumed that the discharge stability and clogging recovery property can be improved (however, the factor is not limited to this).

<Resin particles>
The resin particles of this embodiment contain a fluorine-containing resin, and the fluorine-containing resin is exposed on at least a part of the surface of the resin particles. Specifically, the resin particles of the present embodiment are excellent in heat resistance and solvent resistance because the fluororesin is exposed on at least a part of the surface of the resin particles. Occurrence of fusion and welding is suppressed, and discharge stability is excellent. Moreover, the solvent resistance of the coating film is also good. As the resin particles in which the fluororesin is exposed on at least a part of the surface of the resin particles, for example, in the case of having a core-shell structure including a core resin and a shell resin, which will be described later, at least the shell part is made of a fluororesin. It may be resin particles in which the core resin is completely covered with the shell resin, or resin particles in which a part of the core resin is covered with the shell resin. Moreover, the resin which does not have a core-shell structure may be sufficient. Here, the resin that does not have a core-shell structure includes, for example, a fluororesin that forms resin particles alone or a non-fluororesin that forms resin particles treated with a fluororesin.
The content of the fluorine-containing resin in the resin particles is not particularly limited as long as the fluorine-containing resin can be exposed on at least a part of the surface. However, from the viewpoint of improving both discharge stability and solvent resistance, and also from the viewpoint of improving friction fastness and texture, the content of the fluorine-containing resin is 10% with respect to the total amount of resin particles. % To 95% by mass, more preferably 15% to 90% by mass, and still more preferably 20% to 85% by mass.

  The resin particles of the present embodiment preferably have a core-shell structure including a core resin and a shell resin. Due to the core-shell structure of the resin particles, the core resin flows out from the resin particles attached to the recording medium, and thus the obtained recorded matter tends to have better friction fastness. Further, when the resin particles have a core-shell structure, the fluorine-containing resin is exposed on the surface of the resin particles by being contained in the shell resin. However, the resin particles may be made of a fluorine-containing resin and do not have a core-shell structure. The “core-shell structure” refers to a structure in which the core resin is formed inside the voids of the shell resin. Therefore, not only a structure in which the surface of the core resin is covered with the shell resin but also a structure in which the core resin is filled in a part of the space of the three-dimensional network structure made of the shell resin is included. Therefore, the “core-shell structure” in the present specification includes resin particles in which the boundary between the core portion and the shell portion is not strictly clear.

  The resin that can be contained in the resin particles other than the fluorine-containing resin (for example, the core resin when the resin particles have a core-shell structure and the fluorine-containing resin is contained in the shell resin) is not particularly limited. (Meth) acrylic resin, styrene acrylic resin, fluorene resin, urethane resin, polyolefin resin, rosin modified resin, terpene resin, polyester resin, polyamide resin, epoxy resin, vinyl chloride resin, chloride A vinyl-vinyl acetate copolymer and an ethylene vinyl acetate resin are mentioned. These core resins may be used individually by 1 type, and may use 2 or more types together. Among these, since it has a high degree of freedom in design, it is preferably one or more selected from the group consisting of urethane resins and (meth) acrylic resins, and more preferably includes urethane resins. preferable. By including the urethane-based resin, when the ink composition of the present embodiment is provided for textile printing, the texture tends to be improved.

  The urethane resin is a resin having a urethane bond in the molecule. From the viewpoint of the storage stability of the ink composition, and the viewpoint that the reactivity with the urethane resin is improved when the pretreatment agent described later contains a polyvalent metal compound, the urethane resin is a carboxy group, a sulfo group, or a hydroxy group. It is preferable that it is an anionic urethane type resin which has anionic functional groups, such as.

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.
Examples of urethane resins include, but are not limited to, commercially available products such as Takelac W6110 (manufactured by Mitsui Chemicals), Acrit WBR-022U (manufactured by Taisei Fine Chemical Co., Ltd.), and Permarin UX-368T (polycarbonate, manufactured by Sanyo Chemical Co., Ltd.). ), Uprene UXA-307 (polyester type, manufactured by Sanyo Chemical Co., Ltd.), U-coat UWS-145 (polyester type, manufactured by Sanyo Chemical Co., Ltd.) can be used.

(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”.
The (meth) acrylic resin is not limited to the following, but, for example, commercially available products include ALMATEX H700 (manufactured by Mitsui Chemicals), ALMATEX Z113 (manufactured by Mitsui Chemicals), and ALMATEX Z115 (manufactured by Mitsui Chemicals). Almatex EPG1001 (made by Mitsui Chemicals) can be used.

  The core resin may contain a fluorine-containing resin. However, from the viewpoint of improving the solvent resistance, friction fastness and texture, the content of the fluorinated resin in the core resin is preferably 50% by mass or less, and preferably 30% by mass or less, based on the total amount of the core resin. More preferred is 10% by mass or less. In particular, it is preferable that the core resin does not contain a fluorine-containing resin.

  When the resin particles have a core-shell structure, the shell resin is not particularly limited as long as it contains a fluorine-containing resin, and the same resin as the resin used for the core resin described above may be used in combination.

  The fluorine-containing resin is not particularly limited as long as it has a fluorine atom in its structure. For example, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, polyvinylpolypyrrolidone, polyvinylidene fluoride, Examples thereof include DVDF, tetrafluoroethylene / ethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, and tetrafluoroethylene / hexafluoropropylene copolymer. These fluorine-containing resins may be used alone or in combination of two or more. Among these, from the viewpoint of more reliably achieving the effects of the present invention, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene It is preferable that it is 1 type, or 2 or more types selected from the group which consists of a copolymer, a polyvinylidene fluoride, and an ethylene chlorotrifluoroethylene copolymer.

The polytetrafluoroethylene (PTFE) of this embodiment has a structural unit represented by the following general formula (1).
− (CF ₂ CF ₂ ) _n − (1)
In formula (1), n represents a positive integer. Some of the fluorine atoms (F) represented here may be substituted with a substituent such as an alkyl group.

The tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) of the present embodiment has a structural unit represented by the following general formula (2).
_{- (CF 2 CF 2) m} - (CF 2 CF (OR f)) n - (2)
In formula (2), m and n each represent a positive integer. R _f represents a perfluoroalkyl group. Some of the fluorine atoms (F) represented here may be substituted with a substituent such as an alkyl group.

The tetrafluoroethylene / ethylene copolymer (ETFE) of the present embodiment has a structural unit represented by the following general formula (3).
_{- (CF 2 CF 2) m} - (CH 2 CH 2) n - (3)
In formula (3), m and n each represent a positive integer. Some of the fluorine atoms (F) and hydrogen atoms (H) represented here may be substituted with a substituent such as an alkyl group.

The tetrafluoroethylene / hexafluoropropylene copolymer (FEP) of the present embodiment has a structural unit represented by the following general formula (4).
_{- (CF 2 CF 2) m} - (CF 2 CF (CF 3)) n - (4)
In formula (4), m and n each represent a positive integer. Some of the fluorine atoms (F) represented here may be substituted with a substituent such as an alkyl group.

The polyvinylidene fluoride (PVDF) of this embodiment has a structural unit represented by the following general formula (5).
_{- (CH 2 CF 2) n} - (5)
In formula (5), n represents a positive integer. Some of the fluorine atoms (F) and hydrogen atoms (H) represented here may be substituted with a substituent such as an alkyl group.

The ethylene / chlorotrifluoroethylene copolymer (ECTFE) of the present embodiment has a structural unit represented by the following general formula (6).
_{- (CH 2 CH 2) m} - (CF 2 CFCl) n - (6)
In formula (6), m and n each represent a positive integer. Some of the fluorine atoms (F) and chlorine atoms (Cl) represented here may be substituted with a substituent such as an alkyl group.

  The content of the fluorine-containing resin in the shell resin is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more with respect to the total amount of the shell resin, from the viewpoint of improving discharge stability. Further preferred. In particular, the shell resin is preferably made of a fluorine-containing resin.

  The average particle diameter of the resin particles is preferably 10 nm or more and 400 nm or less, more preferably 40 nm or more and 250 nm or less, and further preferably 80 nm or more and 180 nm or less. Thus, when the average particle diameter of the resin particles is 400 nm or less, the ink composition tends to be more excellent in film formability on the recording medium, and it is difficult to form a large lump even if the resin particles aggregate. Therefore, the nozzle clogging tends to be further suppressed. In addition, when the average particle diameter of the resin particles is 400 nm or less, the viscosity of the ink composition can be relatively increased, and even if the temperature of the ink composition rises in the recording head, the ink discharge performance is not good. It tends to be able to suppress the viscosity from decreasing as it becomes more stable. On the other hand, when the average particle diameter of the resin particles is 10 nm or more, the resin particles tend to be more easily prepared.

  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. As the particle size distribution measuring device, for example, a particle size distribution meter (for example, Microtrac UPA manufactured by Nikkiso Co., Ltd.) using the dynamic light scattering method or Zetasizer Nano manufactured by Spectris Co., Ltd. is used. ZS).

In the resin particles, the thickness of the portion of the fluorine-containing resin contained in the shell resin is preferably 1.0 nm or more and 100 nm or less, more preferably 3.0 nm or more and 50 nm or less, and further preferably 10 nm or more and 25 nm or less. is there. When the thickness is 1.0 nm or more, the ejection stability is excellent, and when the thickness is 100 nm or less, the solvent resistance, friction fastness, and texture can be further improved. This thickness is the thickness of the shell itself when the shell resin is made of a fluorine-containing resin, and when the shell resin contains a fluorine-containing resin and other resins, the fluorine-containing amount relative to the total amount of the shell resin. It is represented by the product of the ratio of the resin content to the 1/3 power and the thickness of the shell portion. The thickness of the portion of the fluorine-containing resin contained in the shell resin is preferably 5% or more and 20% or less of the average particle diameter of the resin particles. If it is 5% or more of the average particle diameter of the resin particles, fusing and welding are preferably suppressed, and the ejection stability tends to be good. There is a tendency for rubbing to be good.
The thickness of the fluororesin portion contained in the shell resin can be measured, for example, by observing the cut surface with a scanning electron microscope (SEM) after cutting the resin particles with a focused ion beam (FIB). it can. When the resin particles are cut with a focused ion beam (FIB), the ink composition may be frozen as necessary to prepare a sample.

  The content of the shell resin in the resin particles is preferably 10% to 95% by volume, more preferably 15% to 90% by volume, and more preferably 20% to 85% by volume with respect to the total amount of the resin particles. Is more preferable. When the content is 10% by volume or more, the ejection stability tends to be better, and when it is 95% by volume or less, the friction fastness tends to be better. The content of the shell resin can be calculated from the thickness of the shell portion and the average particle diameter of the resin particles, assuming that the resin particles have a true spherical shape.

  The content of the resin particles in the ink composition (in terms of solid content) is preferably 1.0% by mass or more and 20% by mass or less, and preferably 4.0% by mass or more and 18% by mass with respect to the total amount (100% by mass) of the ink composition. The mass% is more preferable, and 7.0 mass% or more and 15 mass% or less is more preferable. When the content of the resin particles is 1.0% by mass or more, the friction fastness and adhesion tend to be more excellent. Moreover, it exists in the tendency which is more excellent in discharge stability because content of the resin particle is 20 mass% or less.

<Method for producing resin particles>
The method for producing the resin particles of the present embodiment is not particularly limited, and examples thereof include an emulsion polymerization method using an emulsifier and a method of forming by soap-free polymerization substantially using no emulsifier. And a method of forming resin particles using a shell resin. Soap-free polymerization refers to a polymerization method for producing a core-shell resin without substantially using an emulsifier. As used herein, “emulsifier” means a surfactant used in synthesis. As soap-free polymerization, for example, polymerization of resin particles in the presence of an emulsifier content in a solution of 1% by mass or less can be mentioned. In soap-free polymerization, for example, a shell resin containing a fluorine-containing resin is formed, and a core is formed in the shell resin. Further, when resin particles are produced using soap-free polymerization, the average particle size becomes very small and the ejection stability and glossiness of the ink composition tend to be further improved.

  Although it does not specifically limit as surfactant used for a synthesis | combination, Anionic surfactant and a nonionic surfactant are suitable. Although it does not specifically limit as an anionic surfactant, For example, the ammonium salt of sodium dodecyl benzan sulfonate, sodium laurate, and polyoxyethylene alkyl ether sulfate is mentioned. The nonionic surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, and polyoxyethylene An ethylene alkylamide is mentioned.

  Although it does not specifically limit as a polymerization initiator used by superposition | polymerization, A hydrophilic initiator is used, For example, potassium persulfate, ammonium persulfate, and hydrogen peroxide water are mentioned.

  Although an example of the method of soap free polymerization is demonstrated below, the polymerization method is not restrict | limited to the following. For example, ion-exchanged water and a polymerization initiator are put in a jacketed polymerization reaction tank, the inside of the polymerization tank is depressurized to remove oxygen, and then returned to atmospheric pressure with nitrogen, and the polymerization reaction tank is filled with a nitrogen atmosphere. . Under the nitrogen atmosphere, first, the temperature inside the polymerization reaction tank is set to a predetermined temperature, and then a pre-emulsion solution containing a monomer that is a constituent element of the shell resin is dropped by a predetermined amount to synthesize a shell resin. . Next, using the voids of the obtained shell resin as a polymerization field, the core resin is polymerized to synthesize resin particles according to this embodiment.

<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 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, 440, 465, 61, DF110D, DF110L (trade names 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 triisopropanolamine, 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 the heating step, the dye can be more satisfactorily dyed on the fibers constituting the 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 180 ° C. or lower, more preferably 90 ° C. or higher and 170 ° C. or lower, and further preferably 120 ° C. or higher and 165 ° C. or lower. When the temperature during the heat treatment is within the above range, the dye tends to be more satisfactorily dyed on the fibers constituting the fabric.
The heat treatment time can be appropriately adjusted, but is preferably 20 seconds or more and 20 minutes or less, more preferably 30 seconds or more and 10 minutes or less, and further preferably 40 seconds or more and 5 minutes or less.

[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 may include a fabric (including the fabric itself), and is an absorptive, low absorptive, or non-absorbent recording medium. May be. Of these, the recording medium is preferably a fabric.

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 recorded matter with more excellent color developability and friction fastness. The cloth pretreatment with the pretreatment liquid containing resin particles may be a conventionally known method.
Further, the fabric may be pretreated with a pretreatment agent containing a component capable of aggregating ink such as a polyvalent metal salt compound, a cationic surfactant, or a cationic polymer.

  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. In the following, “resin particles having a core-shell structure” are referred to as “core-shell type resin particles”.

[Material for core resin or shell resin]
Takelac W6110 (urethane resin, trade name manufactured by Mitsui Chemicals)
ACRYT WBR-022U (urethane resin, trade name manufactured by Taisei Fine Chemical Co., Ltd.)
ALMATEX H700 (acrylic resin, trade name manufactured by Mitsui Chemicals)
ALMATEX Z113 (acrylic resin, trade name manufactured by Mitsui Chemicals)
ALMATEX Z115 (acrylic resin, trade name manufactured by Mitsui Chemicals)
ALMATEX EPG1001 (acrylic resin, trade name manufactured by Mitsui Chemicals)
Permarine UX-368T (Polycarbonate, product name manufactured by Sanyo Kasei Co., Ltd.)
Uprene UXA-307 (polyester, trade name manufactured by Sanyo Chemical Co., Ltd.)
U-coat UWS-145 (polyester, trade name manufactured by Sanyo Kasei Co., Ltd.)
PTFE (Polytetrafluoroethylene)
PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer)
PVPP (polyvinylpolypyrrolidone)
PVDF (polyvinylidene fluoride)
PCTFE (Polychlorotrifluoroethylene)
ETFE (tetrafluoroethylene / ethylene copolymer)
ECTFE (ethylene / chlorotrifluoroethylene copolymer)
FEP (tetrafluoroethylene / hexafluoropropylene copolymer)
PS (polystyrene)

[Preparation of core-shell type resin particles]
Fluoroethercarboxylic acid CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ COONH ₄ 5.3 parts by mass was placed in a 1 L stainless steel autoclave and degassed in vacuum, followed by 450 parts by mass of ion-exchanged water, “Takelac W6110” (Urethane resin, trade name, manufactured by Mitsui Chemicals) 150 parts by mass are sucked and injected. Next, tetrafluoroethylene (TFE) was introduced thereto until the pressure reached 0.01 MPa, and the autoclave was heated and stirred so that the internal temperature of the autoclave was uniformly 50 ° C. After the internal temperature reached 50 ° C., TFE was further introduced until it reached 1.25 MPa, and 20 parts by mass of a 3.6% by mass aqueous solution of ammonium persulfate was added to the autoclave through the press-fitting tube to initiate polymerization. . During the reaction, TFE was continuously introduced from outside the system, and the pressure was maintained at 1.25 MPa. Two hours after the start of the reaction, unreacted TFE was released out of the system to complete the polymerization. Then, it concentrated using the evaporator. Furthermore, by neutralizing with sodium hydroxide and adjusting the pH to the range of 8 to 8.5 and filtering through a 0.3 μm filter, the core shell having Takelac W6110 as the core resin and PTFE as the shell resin An aqueous dispersion of resin particles (resin particles for ink composition) was prepared.

  Further, the constituent materials of the core resin and the shell resin shown in Table 1 and Table 2 are changed so that the shell thickness (shell thickness) and the average particle diameter (average particle diameter) shown in Table 1 and Table 2 are obtained. Resin particles used in each ink composition were prepared in the same manner as the resin particles used in ink composition 1 except that the amount used and the polymerization reaction time were adjusted. The resin particles used in the ink compositions 27, 29, and 31 in which the material constituting the shell resin is not described are polymerized in a single step without polymerizing the shell resin to prepare a single layer. Resin particles were prepared.

[Average particle size]
The resin particles obtained above were measured by “Zeta Sizer Nano ZS” (Spectris Co., Ltd.) to determine the average particle diameter φ (nm) of the core-shell type resin particles.

[Thickness of shell]
After freezing the ink composition and cutting the resin particles with a focused ion beam (FIB), the cut surface was observed with a scanning electron microscope (SEM), and the thickness of the shell was measured.

[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]
C. I. Pigment Blue 15: 3
C. I. Pigment Yellow 74
C. I. Pigment Red 254
C. I. Pigment Black 7
TiO ₂
[Resin particles]
Each resin particle shown in Table 1 and Table 2 [Organic solvent]
Glycerol 1,2-hexanediol (abbreviated as “1,2-HD” in the table)
1,3-propanediol (abbreviated as “1,3-PD” in the table)
Polyethylene glycol (average molecular weight 200, abbreviated as “PEG200” in the table)
Triethylene glycol monobutyl ether (abbreviated as “TEGmBE” in the table)
2-pyrrolidone (abbreviated as “2-P” in the table)
[Surfactant]
Surfynol DF110D (trade name, manufactured by Nissin Chemical Industry CO., Ltd.)
Surfynol DF110L (Nissin Chemical Industry CO., Ltd. product name)
Surfynol 104 (trade name, manufactured by Nissin Chemical Industry CO., Ltd.)
Surfynol 440 (trade name, manufactured by Nissin Chemical Industry CO., Ltd.)
Orphin E1010 (trade name, manufactured by Air Products Japan, Inc.)
[Others]
Silface SAG503A (product name, silicone emulsion Nissin Chemical Industry CO., Ltd.)
Triisopropanolamine (abbreviated as “TIPA” in the table)
Pure water

[Preparation of ink composition]
Each material was mixed with the composition shown in Table 1 and Table 2 below, and stirred sufficiently to obtain an ink composition. In Tables 1 and 2 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 composition prepared above was recorded on 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 obtained are shown in Table 3.
(Evaluation criteria)
A: There was no clogging or clogging disappeared by performing head cleaning once.
B: The clogging did not disappear even if the head cleaning was performed once, but disappeared by performing the head cleaning twice.
C: The clogging did not disappear even if the head cleaning was performed twice, but disappeared by performing the head cleaning three times.
E: The clogging did not disappear even after performing the head cleaning three times.

[Solvent resistance]
For each printed product, dry cleaning is performed according to Method A of “Dye Fastness Test for Dry Cleaning (JIS L 0860)”, and the image density (initial value, OD value) and dry cleaning of each printed product before dry cleaning are performed. The back image density (OD value) was measured using a Macbeth densitometer (manufactured by Macbeth, “TD-931”), and the solvent resistance was evaluated according to the following evaluation criteria. The results are shown in Table 3.
(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 E: Image density after washing is less than 70% before washing

[Friction fastness]
A strip-shaped test piece for abrasion resistance was cut out from each printed matter. Using the above test pieces, friction fastness evaluation was performed with a Gakushin type frictional fastness tester AB-301S (trade name, Tester Sangyo Co., Ltd.). The test conditions were carried out in accordance with JIS L 0849, using an opposing cloth as a gold width, applying 150 reciprocating friction slides at a load of 200 g. The test results in the drying mode (the facing fabric was dry) were evaluated according to the following evaluation criteria. The results are shown in Table 3.
(Evaluation criteria)
A: As for the degree of color transfer to the gold width and peeling of the ink in the printed part, there is no color transfer in the gold width, and there is no peeling or scratching of the ink in the printed part. B: Ink in the printed part has a small amount of color transfer. C: There is a medium color transfer in the gold width, and there is a small amount of peeling and scratches on the printed part in a line E: There is a large amount of color transfer in the gold line, Peeling or scratches on the surface

[Texture]
The texture was evaluated according to the following evaluation criteria. The results are shown in Table 3.
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.
E: The touch of the printed material was clearly harder than the original fabric.

Claims (10)

A colorant, water, an organic solvent, and resin particles containing a fluorine-containing resin,
The ink-jet ink composition, wherein the resin particles have the fluororesin exposed on at least a part of the surface of the resin particles.   The fluororesin includes polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, polyvinylidene fluoride, and ethylene / The inkjet ink composition according to claim 1, wherein the inkjet ink composition is one or more selected from the group consisting of chlorotrifluoroethylene copolymers. The resin particles have a core-shell structure including a core resin and a shell resin,
The inkjet ink composition according to claim 1, wherein the shell resin includes the fluorine-containing resin.   The inkjet ink composition according to claim 3, wherein a thickness of a part of the fluorine-containing resin contained in the shell resin is 1.0 nm or more and 100 nm or less.   The inkjet ink composition according to claim 3 or 4, wherein the core resin contains a urethane resin.   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 400 nm or less.   Content of the said resin particle is 1.0 mass% or more and 20 mass% or less in conversion of solid content with respect to the total amount of the said inkjet ink composition, It is any one of Claims 1-6. Inkjet ink composition.   The ink-jet ink composition according to claim 1, wherein the colorant is a pigment or a dye.   The inkjet ink composition according to any one of claims 1 to 8, wherein a content of the coloring material is 0.3% by mass or more and 5.0% by mass or less with respect to a total amount of the inkjet ink composition. object. Recording the inkjet ink composition according to any one of claims 1 to 9 on a recording medium to obtain a recorded matter;
And a step of heating the recorded matter.

Images