JP2017190369A - Inkjet ink composition, and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet ink composition that prevents clogging in a discharge nozzle while maintaining excellent discharge stability.SOLUTION: An ink jet ink composition contains a colorant, water, an organic solvent and a resin particle. The resin particle is a resin particle containing a resin having a hydrophilic block in a side chain.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 a case where high ejection stability is achieved even when used in an inkjet recording method that has excellent dispersion stability and is ejected by applying thermal energy to ink, and glossy paper is used. However, for the purpose of providing an inkjet pigment ink capable of forming an image with sufficient scratch resistance, a hydrophobic segment comprising a pigment, water, a graft copolymer, and a water-soluble organic solvent, and constituting the graft copolymer, Disclosed is an inkjet pigment ink obtained by copolymerizing a monomer having an aromatic ring and a monomer having an anionic functional group, and by polymerizing a monomer having an anionic functional group in the hydrophilic segment constituting the graft copolymer. ing.

JP 2008-143987 A

  However, when the inkjet pigment ink disclosed in Patent Document 1 is used, high ejection stability can be realized, but the graft copolymer contained in the ink with respect to the nozzle surface of the ejection nozzle that ejects the ink. As a result, the discharge nozzle is clogged.

  Accordingly, the present invention has been made to solve at least a part of the above-described problems, and an ink-jet ink composition that easily eliminates clogging generated in a discharge nozzle while maintaining excellent discharge stability. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the inventors of the present invention include an ink jet including a coloring material, water, and resin particles, and the resin particles include a resin particle containing a resin having a hydrophilic block in a side chain. By using the ink composition, it was found that the discharge stability and clogging recovery property were excellent, and the present invention was completed.

  That is, the present invention is an ink-jet ink composition comprising a color material, water, and resin particles, wherein the resin particles comprise resin particles containing a resin having a hydrophilic block in a side chain. 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-jet ink composition according to the present invention mainly includes resin particles containing a resin having a hydrophilic block in the side chain, thereby improving the dispersibility of the resin particles in water and having a low viscosity. As a result, in addition to excellent ejection stability, excellent clogging recovery can be obtained.

  Further, in the ink composition according to the present invention, the content of the organic solvent having a standard boiling point of 280 ° C. or more is preferably 3.0% by mass or less based on the total amount of the inkjet ink composition, It is preferably used in a method for recording the inkjet ink composition on the recording medium, and the content of the resin particles is 0.5% by mass or more and 20% by mass with respect to the total amount of the inkjet ink composition. Preferably, the hydrophilic block is one or more selected from the group consisting of polyvinyl alcohol resin, polyethylene glycol, polyphenylene oxide, polyvinyl propylene, and polyacrylamide, and the resin particles The average particle diameter is preferably 100 nm or more and 1000 nm or less. Preferably to include in the colorant, preferably a pigment and / or dye.

  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.

It is a flowchart which shows an example of the recording 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 acid” means both acrylic acid and methacrylic acid 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.

[Inkjet ink composition]
The ink-jet ink composition of the present embodiment (hereinafter also simply referred to as “ink composition”) includes a coloring material, water, and resin particles. Moreover, the said resin particle contains the resin particle containing resin which has a hydrophilic block in a side chain. By using such an ink composition, excellent ejection stability and clogging recovery properties can be obtained. The factors are 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 a hydrophilic block in the side chain, thereby improving the dispersibility of the resin particles in water and having a low viscosity. As a result, in addition to excellent ejection stability, excellent clogging recovery can be obtained.

<Color material>
The color material of this embodiment can contain a pigment and / 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.

  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.

  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. Direct Blue 199, 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, 95,297,301,315,330,333,359,360 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 0.2% 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>
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.

<Organic solvent>
The ink composition of this embodiment can further contain an organic solvent. An organic solvent will not be specifically limited if it is an organic solvent which can be used with water. Further, the content of the organic solvent having a standard boiling point of 280 ° C. or more is preferably 3.0% by mass or less, more 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, still more preferably 0.2% by mass or less, and further preferably 0.1% by mass or less. Due to the fact that the organic solvent having a standard boiling point of 280 ° C. or higher does not contain more than 3.0% by mass, it is possible to obtain a higher level of drying property of the ink composition landed on the recording medium. , Excellent abrasion resistance tends to be obtained. This factor is inferred as follows (however, the factor is not limited to this). In general, when an ink jet ink composition is applied on a low-absorbency recording medium or a non-absorbing recording medium, heating (for example, 40 to 50) is performed to suppress a bleeding phenomenon on the recording medium. In order to maintain ejection stability and clogging recovery even under such a heating environment, an organic solvent having a normal boiling point of 280 ° C. or higher may be used. It may be contained in the composition. However, such an organic solvent having a normal boiling point of 280 ° C. or more tends to remain in the recording medium, and may cause a decrease in abrasion resistance. According to the ink composition of the present embodiment, the content of the organic solvent having a standard boiling point of 280 ° C. or higher is 3.0% by mass by including resin particles mainly containing a resin having a hydrophilic block in the side chain. Even in the following cases, the ejection stability and clogging recovery can be improved, and the abrasion resistance can also be improved.

  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. Further, the ink composition particularly preferably does not contain an organic solvent having a standard boiling point of 280 ° C. or higher. This is particularly preferable when the recording medium is a low-absorbing recording medium or a non-absorbing recording medium. Examples of the organic solvent having a standard boiling point of 280 ° C. or higher include glycerin. When the recording medium is a fabric, a larger amount of resin particles (for example, 20% by mass) may be used for the purpose of improving friction fastness, in which case the standard boiling point is 280 ° C. or higher. It may contain an 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 pyrrolidone, imidazolidinone, sulfoxide, lactone, and amide ether solvents. Specifically, among these, 2-pyrrolidone, N-alkyl-2-pyrrolidone, 1-alkyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, imidazole, 1 -Methylimidazole, 2-methylimidazole, and 1,2-dimethylimidazole are preferred.

  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, 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 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 “emulsion”) are resin particles containing a resin having a hydrophilic block in the side chain, and are hydrophilic to the main chain in the resin constituting the resin particle. Resin particles grafted with resin. By polymerizing a polymerizable unsaturated monomer in the presence of a polymerization initiator in an aqueous emulsion containing a hydrophilic resin, the hydrophilic resin is grafted to the resin particles obtained by polymerizing the polymerizable unsaturated monomer. Resin particles can be produced. When a hydrophilic resin is present in the polymerization system, the hydrophilic resin has an effective function as an emulsifier for polymerization, and when the ink composition containing the obtained polymer particles is used, it has a water dispersibility. Due to the improvement and the low viscosity, the discharge stability and clogging recovery are excellent. Here, the term “grafted” includes not only covalent bonding to the surface of the resin particles but also non-covalent bonding such as electrostatic bonding force and van der Waals force. is there. The “side chain” includes not only a covalent bond to the main chain but also a non-covalent bond such as electrostatic bond or van der Waals. Here, the main chain is a polymer obtained by polymerizing a polymerizable unsaturated monomer, and the side chain is a hydrophilic resin.

  The polymerizable unsaturated monomer is not particularly limited as long as it can form resin particles, but is preferably more hydrophobic than the resin constituting the hydrophilic block. For example, (meth) acrylic acid esters , Vinyl esters, vinyl ethers, aromatic vinyl compounds, unsaturated carboxylic acid amides, olefins, dienes, and unsaturated nitriles. These polymerizable unsaturated monomers can be used singly or in combination of two or more.

  Although it does not specifically limit as (meth) acrylic acid ester, All the conventionally well-known (meth) acrylic acid esters can be used. As typical examples, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate (for example, n-butyl acrylate), hexyl (meth) acrylate (Meth) acrylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; (Meth) hydroxyethyl acrylate, hydroxyalkyl acrylate such as hydroxypropyl (meth) acrylate, methoxymethyl acrylate, alkoxyalkyl (meth) acrylate such as ethoxymethyl (meth) acrylate, glycidyl (meth) acrylate, (Meth) acrylic acid and polyoxyethylene Recall, esters of polyoxyalkylene glycols such as polyoxypropylene glycol (acryloyl compound having a polyoxyalkylene structure, or methacryloyl compound) containing the reactive functional group such as (meth) acrylic acid esters. In the present specification, “(meth) acryl” is a concept including both “methacryl” and “acryl”.

  Although it does not specifically limit as vinyl ester, All the conventionally well-known vinyl esters can be used. As representative examples, for example, vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl octylate, Veova 10 (trade name: Examples thereof include vinyl esters of aliphatic carboxylic acids having 3 to 18 carbon atoms such as Shell Japan; and vinyl aromatic carboxylic acids such as vinyl benzoate.

  Any conventionally known vinyl ethers can be used as the vinyl ethers. Typical examples include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, and tert-amyl vinyl ether.

  Although it does not specifically limit as an aromatic vinyl compound, All the conventionally well-known aromatic vinyl compounds can be used. Typical examples include styrene, divinylbenzene, vinyltoluene, α-methylstyrene, N-vinylpyrrolidone, vinylpyridine, and the like. Unsaturated carboxylic acid amides include (meth) acrylamides such as (meth) acrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, and N-methoxybutylacrylamide.

  The olefins are not particularly limited, and any conventionally known olefins can be used. Typical examples include ethylene, propylene, butylene, isobutylene, and pentene.

  Although it does not specifically limit as dienes, All the conventionally well-known dienes can be used. Typical examples include butadiene, isoprene, and chloroprene.

  Although it does not specifically limit as unsaturated nitriles, Any of conventionally well-known unsaturated nitriles can be used. A typical example is (meth) acrylonitrile.

  Of these polymerizable unsaturated monomers, one or more selected from the group consisting of (meth) acrylic acid esters and aromatic vinyl compounds from the viewpoint of more effectively and reliably achieving the effects of the present invention. Two or more are preferably used.

  When two or more kinds of polymerizable unsaturated monomers are used in combination, the respective polymerizable unsaturated monomers may be added to the system at different timings. May be. The polymerizable unsaturated monomer may be added to the system after previously mixed and emulsified with a hydrophilic resin.

  The hydrophilic resin (hereinafter also referred to as “hydrophilic block”) is not particularly limited. For example, polyvinyl alcohol resin (PVA resin) such as polyvinyl alcohol (PVA); polyethylene glycol, polyphenylene oxide; methyl cellulose, ethyl cellulose , Cellulose derivatives such as hydroxymethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, aminomethylhydroxypropylcellulose, aminoethylhydroxypropylcellulose; starch, tragacanth, pectin, glue, alginic acid or a salt thereof, gelatin, Polyvinylpyrrolidone, polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, poly (meth) a Copolymers of rilamide, vinyl acetate and unsaturated acids such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid; copolymers of styrene and the above unsaturated acids, vinyl ethers And a copolymer of the unsaturated acid and salts or esters of the copolymer. These hydrophilic resins can be used singly or in combination of two or more.

  Among the hydrophilic resins described above, one or more selected from the group consisting of PVA-based resin, polyethylene glycol, polyphenylene oxide, polyvinyl pyrrolidone, and polyacrylamide, the viewpoint of more reliably exhibiting the effects of the present invention, And from the viewpoint of easier adjustment of the viscosity.

  The content of the hydrophilic resin can be appropriately selected within a range that does not impair the polymerizability at the time of copolymerization and the ejection stability when the ink composition is used. However, from the viewpoint of more effectively and reliably achieving the effects of the present invention, it is preferably 0.01% by mass or more and 40% by mass with respect to the total amount (100% by mass) of the total resin (total solid content) in the obtained resin particles. It is not more than mass%, more preferably not less than 0.1 mass% and not more than 20 mass%, still more preferably not less than 0.5 mass% and not more than 10 mass%.

  As said PVA-type resin, the PVA-type resin which has the following specific average saponification degree and average polymerization degree is more preferable.

  The average saponification degree of the PVA-based resin is preferably 70 mol% or more and 99.9 mol% or less, more preferably 80 mol5 or more and 99.5 mol% or less, and further preferably 85 mol% or more and 99.99 mol% or less. 0 mol% or less. When the average saponification degree is 70 mol% or more, the polymerization proceeds stably, and after the polymerization is completed, the storage stability of the re-emulsifiable synthetic resin powder after spray drying tends to suppress a decrease, When the average saponification degree is 99.9 mol% or less, re-emulsification tends to be facilitated. The average saponification degree can be determined according to the saponification degree calculation method described in JIS K 6726.

  The average degree of polymerization of the PVA-based resin is preferably 50 or more and 3000 or less, more preferably 200 or more and 2000 or less, and further preferably 300 or more and 1000 or less. When the average degree of polymerization is 50 or more, the protective colloid ability at the time of emulsion polymerization becomes sufficient, and the polymerization tends to proceed stably. When the average degree of polymerization is 3000 or less, the viscosity increases during the polymerization. The reaction system is unlikely to become unstable and tends to suppress a decrease in dispersion stability. The average degree of polymerization can be determined according to the method for calculating the average degree of polymerization described in JIS K 6726.

  The PVA-based resin means PVA itself or one modified with, for example, various modified species. The degree of modification is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less.

  The modified PVA resin is not particularly limited. For example, anion-modified PVA resin modified with an anionic group including a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and a cationic property such as a quaternary ammonium group. Cation modified PVA resin modified with a group; modified PVA resin modified with various functional groups such as acetoacetyl group, diacetone acrylamide group, mercapto group, silanol group, etc .; 1,2-diol in the side chain PVA-based resin having a bond is exemplified. In view of excellent emulsification stability, anion-modified PVA, particularly a modified PVA-based resin modified with a sulfonic acid group is more preferable.

  Examples of the PVA resin having a 1,2-diol bond in the side chain include a PVA resin containing a 1,2-diol structural unit represented by the following formula (1).

  Such PVA-based resins include, for example, (I) a method of saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene, and (II) a copolymer of vinyl acetate and vinyl ethylene carbonate. Saponification and decarboxylation, (III) saponification and deketalization of a copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane, or (IV) acetic acid It can be obtained by a method of saponifying a copolymer of vinyl and glyceryl monoallyl ether.

  The 1,2-diol bond amount of the PVA resin is preferably 1.0 mol% or more and 15 mol% or less, more preferably 1.0 mol% or more and 12 mol% or less, and further preferably 2.0 mol% or less. It is from mol% to 10 mol%, more preferably from 2.0 mol% to 9.0 mol%. Here, the 1,2-diol bond amount is, for example, represented by the above formula (1) contained in the PVA resin when the 1,2-diol structural unit is represented by the above formula (1). It means the molar ratio of 1,2-diol bonded structural units. When the 1,2-diol bond amount is 1.0 mol% or more, the mechanical stability of the resin particles and the water resistance of the film tend to be high, and when it is 15 mol% or less, the stability during polymerization is increased. There is a tendency that stable resin particles having a high non-volatile content can be obtained more easily. In addition, a non-volatile content means the residue which remained after heat-drying an emulsion, and the mass before and behind heat-drying can be calculated | required according to the calculation method as described in JISK6828-1.

  As the water-soluble resin, an unmodified type partially / saponified PVA resin or various modified types / completely saponified PVA resins may be used in combination.

  The polymerization initiator is not particularly limited, and is a conventional initiator, for example, organic peroxides such as hydrogen peroxide and benzoyl peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile and the like. Can be used. These initiators can also be used as redox initiators in combination with a reducing agent such as tartaric acid, Rongalite, sodium bisulfite, and ascorbic acid. The amount of the polymerization initiator used is preferably 0.05% by mass or more and 2.0% by mass or less with respect to the total amount (100% by mass) of the polymerizable unsaturated monomer. Moreover, the usage-amount of the reducing agent at the time of using a redox-type initiator can be suitably set according to the kind etc. of a polymerization initiator.

  Further, a chain transfer agent may be further used. Examples of the chain transfer agent include alcohols such as methanol, ethanol, propanol and butanol; aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, furfural and benzaldehyde; and dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycol Examples include mercaptans such as acid, octyl thioglycolate, and thioglycerol. These can be used individually by 1 type or in combination of 2 or more types.

  The polymerization apparatus is not particularly limited, and an atmospheric emulsion polymerization apparatus or the like that is routinely used in the industry can be used. The polymerization temperature is preferably 60 to 90 ° C, more preferably 70 to 85 ° C.

  For resin particles, other resins and surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, etc.), etc., as long as the polymerizability and performance as an ink composition are not impaired. May be added. The content of the surfactant is, for example, preferably 0.1% by mass or more and 10% by mass or less, more preferably as the content (solid content conversion) in the total resin (total solid content) of the obtained resin particles. Is 0.2 mass% or more and 8.0 mass% or less.

  Any surfactant can be used as long as it is known to those skilled in the art for use in emulsion polymerization. Therefore, the surfactant can be appropriately selected from known ones such as anionic, cationic and nonionic surfactants.

  Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and nonionic surfactants such as those having a pluronic structure and those having a polyoxyethylene structure. Agents. Moreover, the reactive surfactant which has a radically polymerizable unsaturated bond in a structure can also be used as a surfactant. These may be used alone or in combination of two or more.

  The use of the surfactant has an effect of facilitating the emulsion polymerization, making it easy to control (effect as an emulsifier), and suppressing the generation of coarse particles and block-like substances generated during the polymerization. However, if many of these surfactants are used as emulsifiers, the graft rate tends to decrease. For this reason, when using a surfactant, it is desirable that the amount used is an auxiliary amount with respect to the PVA resin, that is, as small as possible.

  The average particle size of the resin particles is preferably 100 nm or more and 1000 nm or less, more preferably 200 nm or more and 800 nm or less, and further preferably 350 nm or more and 650 nm or less. As described above, when the average particle diameter of the resin particles is 1000 nm or less, excellent glossiness of the recorded material is easily obtained, and the film forming property of the ink composition on the recording medium tends to be excellent. Further, when the average particle diameter of the resin particles is 1000 nm or less, it is difficult to form a large lump even if agglomeration occurs, so that clogging of the nozzle tends to be further suppressed. On the other hand, when the average particle diameter of the resin particles is 100 nm or more, the viscosity of the ink composition can be kept low, the ejection stability becomes good, and the resin particles tend to be prepared more easily.

  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 the resin particles in the ink composition (in terms of solid content) is preferably 0.5% by mass or more and 20% by mass or less, and 1.0% by mass or more and 10% by mass with respect to the total amount (100% by mass) of the ink composition. More preferably, it is 1.5 mass% or less, and more preferably 1.5 mass% or more and 5.0 mass% or less. When the content of the resin particles is 0.5% by mass or more, it tends to be more excellent in abrasion resistance and adhesion. Moreover, it exists in the tendency which is more excellent in discharge stability because content of the resin particle is 20 mass% or less. When used in a textile printing method, a larger amount of resin particles (for example, 20% by mass) may be used for the purpose of improving friction fastness and the like. According to this, the discharge stability and clogging recovery tend to be good.

<Crosslinking agent>
The ink composition of the present embodiment preferably further contains a cross-linking agent. By including a crosslinking agent, the resin particles tend to be more excellent in abrasion resistance and friction fastness due to crosslinking between the resin particles. In addition, the storage stability tends to be excellent. The cross-linking agent is not particularly limited as long as the resin particles can be cross-linked, and examples thereof include a blocked isocyanate type polyisocyanate cross-linking agent.

  In the blocked isocyanate type polyisocyanate type crosslinking agent, the active isocyanate group is protected by the blocking agent and remains stable in the normal state, but the blocking agent is dissociated by heat treatment, and the active isocyanate group is regenerated, thereby causing a crosslinking reaction. do. Specific examples of such a crosslinking agent include Elastolon BN-69, 11 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., SU-268A, NBP-8730, NBP-211 manufactured by Meisei Chemical Industry Co., Ltd., and the like. These crosslinking agents may be used individually by 1 type, and may use 2 or more types together.

  In addition, when the polymerizable unsaturated monomer contains (meth) acrylic acid, carbodiimide or oxazoline, which are crosslinking agents that react with carboxylic acid, can be used. Examples of carbodiimide include Carbodilite E-02 and E-03A manufactured by Nisshinbo Chemical Co., Ltd., and examples of oxazoline include Epoxy K-2010E, K-2020E and K-2030E manufactured by Nippon Shokubai Co., Ltd.

<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 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 recording method of the present embodiment. As shown in FIG. 1, the recording method of this embodiment may further include the following heating step. Moreover, the textile printing method of this embodiment may further have the following washing | cleaning process other than the following heating process.

  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. Hereinafter, the ink jet recording method will be described in detail by taking each step of the ink jet textile printing method as an example.

[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 recording method of the present embodiment may further include a heating step of heating the recording medium to which the ink composition is adhered after the recording step. In the case of the textile printing method, the dye can be satisfactorily dyed on the fibers constituting the fabric by having a heating step. 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 within the above range, the dye 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 manner, a recorded matter such as a printed matter in which an image derived from the above ink composition is formed on a recording medium containing a fabric can be obtained.

<Recording medium>
The recording medium of the present embodiment is not particularly limited, and examples thereof include an absorptive, low absorptive, or nonabsorbable recording medium. Moreover, when using for a textile printing method, it is a thing containing a cloth (fabric itself). Among these, the recording medium is preferably a low absorption recording medium or a non-absorbing recording medium.

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 friction fastness.

  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 emulsion obtained below was measured by “Microtrac UPA” (Nikkiso Co., Ltd.).

[Synthesis Example 1] Emulsions 1-1, 1-2, 1-3
Into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 540 parts by mass of water was added, and as a hydrophilic resin, polyvinyl alcohol (PVA) (product name “OKS-6026, manufactured by Nippon Synthetic Chemical Co., Ltd.) was used. ] 23 parts by mass and 1 part by mass of baking soda were added and dissolved, and kept at 80 ° C. After PVA is completely dissolved, a catalyst (a solution in which 2 parts by mass of potassium persulfate (KPS) is dissolved in 25 parts by mass of water), 40 parts by mass of a styrene monomer, and n-butyl acrylate (BA) are dissolved in this solution. A mixed solution of 330 parts by mass of the monomer was continuously dropped from separate dropping tanks over 2 hours. After completion of the dropwise addition, the mixture was further stirred for 1.5 hours to complete the polymerization, and a styrene-acrylic copolymer resin emulsion (Emulsion 1-1, average particle size: 500 nm) was obtained. Moreover, the emulsion 1-2 (average particle diameter: 100 nm) and the emulsion 1-3 (average particle diameter 1000 nm) were obtained by adjusting the stirring time after completion | finish of dripping in said synthesis conditions.

[Synthesis Example 2] Emulsion 2
A styrene-acrylic copolymer resin was prepared in the same manner as in Synthesis Example 1 except that polyvinylpyrrolidone (PVP) (product name “K-90”, manufactured by Nippon Shokubai Co., Ltd.) was used instead of PVA as the hydrophilic resin. A system emulsion (Emulsion 2, average particle size: 500 nm) was obtained.

[Synthesis Example 3] Emulsion 3
Styrene was synthesized in the same manner as in Synthesis Example 1 except that polyacrylamide (PAAm) (product name “DK Dry Capsule GB-T”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as the hydrophilic resin instead of PVA. -An acrylic copolymer resin emulsion (Emulsion 3, average particle size: 500 nm) was obtained.

[Synthesis Example 4] Emulsion 4
Into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 540 parts by mass of water was added, and as a hydrophilic resin, polyvinyl alcohol (PVA) (product name “OKS-6026, manufactured by Nippon Synthetic Chemical Co., Ltd.) was used. ] 23 parts by mass and 1 part by mass of baking soda were added and dissolved, and kept at 80 ° C. After PVA is completely dissolved, a catalyst (a solution in which 2 parts by mass of potassium persulfate (KPS) is dissolved in 25 parts by mass of water), 40 parts by mass of a styrene monomer, and n-butyl acrylate (BA) are dissolved in this solution. A mixed solution of 310 parts by mass of monomer and 20 parts by mass of acrylic acid was continuously added dropwise from a separate dropping tank over 2 hours. After completion of dropping, the mixture was further stirred for 1.5 hours to complete the polymerization, and a styrene-acrylic copolymer resin emulsion (emulsion 4, average particle size: 500 nm) was obtained.

[Synthesis Example 5] Emulsion 5
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 540 parts by mass of water was added, and 2 parts by mass of a catalyst (potassium persulfate (KPS)) was added and dissolved therein, and kept at 80 ° C. After KPS was completely dissolved, a mixed solution of 330 parts by mass of styrene monomer and 33 parts by mass of divinylbenzene (DVB) monomer was continuously dropped into this solution from a dropping tank over 2 hours. After the completion of dropping, 40 parts by mass of glycidyl methacrylate (GMA) was continuously dropped from another dropping tank over 2 hours. After the completion of dropping, 10 parts by mass of thiol-terminated polyethylene glycol (PEG) dissolved in water from another dropping tank was continuously dropped over 2 hours. Thereafter, the mixture was stirred for 1.5 hours to complete the polymerization, and an emulsion 5 (average particle size: 500 nm) was obtained.

[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. Direct Blue 199
[Resin particles]
Emulsion 1-1, 1-2, 1-3, 2-5
Emulsion 6 (styrene acrylic resin, trade name “Joncrill 450” manufactured by BASF)
Water-soluble resin (polyvinyl acrylic acid, manufactured by Kuraray Co., Ltd.)
[Crosslinking agent]
ELASTRON BN-11 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Carbodilite E-02 (trade name, manufactured by Nisshinbo Chemical Co., Ltd.)
〔Organic solvent〕
1,2-hexanediol (standard boiling point: 223 ° C)
Propylene glycol (standard boiling point: 188 ° C)
2-pyrrolidone (standard boiling point: 245 ° C)
Glycerin (standard boiling point: 290 ° C)
[Surfactant]
Olfin E1010 (trade name, manufactured by Air Products)
[PH adjuster]
Triisopropanolamine (Anti-mold / preservative)
Proxel XL2 (trade name, manufactured by Arch Chemicals)

[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%.

〔viscosity〕
The viscosity [mPa · s] at 20 ° C. of the prepared ink composition was measured using a cone (diameter: 75 mm, angle: 1 °) with a viscometer (manufactured by Physica, trade name “MCR-300”), and the rotation speed was 100 rpm. As measured.

[Preparation of recorded material]
An ink jet printer, which is a modified machine of PX-G930 (trade name, manufactured by Epson Corporation) with a heater attached to the platen, was prepared. Next, the ink compositions 1 to 13 filled in the recording head were inkjet-coated on a vinyl chloride film at a resolution of 720 × 720 dpi, an amount of 12 mg / inch ² and a platen heated at 45 ° C. to obtain a recorded matter. It was. Thereafter, the recording medium was discharged from the printer, and the recording medium was left standing in an environment of 80 ° C. for 10 minutes and dried (secondary heating).

[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 recorded matter] or [Preparation of printed matter], clogging of the nozzle was confirmed, and ejection stability was evaluated according to the following evaluation criteria. The obtained results are shown in Tables 3 and 4.
(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.

[Storage stability]
The ink composition was stored in an ink container (polyethylene film container) of an ink jet printer (manufactured by Seiko Epson Corporation, product name “PX-G930”), subjected to an acceleration test at 60 ° C. for 7 days, and then at 20 ° C. The viscosity of the ink composition was measured, the thickening rate (ink viscosity at 20 ° C. after the acceleration test / ink viscosity at 20 ° C. before the acceleration test × 100) was determined, and the storage stability was evaluated according to the following evaluation criteria. The obtained results are shown in Tables 3 and 4.
(Evaluation criteria)
A: Less than 1% B: 1% or more and less than 3% C: 3% or more

[Clogging recovery (clogging resistance)]
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 for 1 month at room temperature. 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 obtained results are shown in Tables 3 and 4.
(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 defective nozzles and the number of nozzles whose ejection directions are shifted are 1 to 5 with respect to the total number of nozzles.
C: The number of defective nozzles and the number of nozzles whose ejection directions are shifted are 6 or more with respect to the total number of nozzles.

[Abrasion resistance]
The recorded matter obtained as described above is a friction piece in which a white cotton cloth (JIS L 0803 compliant) is attached to a Gakushin type friction fastness tester AB-301 (trade name, manufactured by Tester Sangyo Co., Ltd.), and a load of 300 g. Until the recorded material was peeled off or rubbed 30 times. Then, scratches and peeling of the recorded matter on the recording medium were visually observed, and the abrasion resistance was evaluated according to the following evaluation criteria. The results obtained are shown in Table 3.
(Evaluation criteria)
A: No scratches or peeling of recorded material was observed.
B: Scratches or peeling of the recorded matter was observed in less than 20% of the rubbed area (stroke area).
C: Scratches or peeling of recorded matter was observed in 20% or more and less than 50% of the rubbed area (stroke area).
D: Scratches or peeling of the recorded matter was observed in 50% or more and less than 90% of the rubbed area (stroke area).
E: Scratches or peeling of the recorded matter was observed in 90% or more of the rubbed area (stroke area).

[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 Table 4.
(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 less than 70% before washing

Claims (9)

Including a coloring material, water, and resin particles,
The said resin particle is an inkjet ink composition containing the resin particle containing resin which has a hydrophilic block in a side chain.   2. The inkjet ink composition according to claim 1, wherein the content of the organic solvent having a standard boiling point of 280 ° C. or more is 3.0% by mass or less based on the total amount of the inkjet ink composition.   The inkjet ink composition of Claim 1 or 2 used for the method of recording the said inkjet ink composition on the recording medium containing a fabric.   The inkjet ink composition according to any one of claims 1 to 3, wherein a content of the resin particles is 0.5% by mass or more and 20% by mass or less with respect to a total amount of the inkjet ink composition.   The hydrophilic block is one or two or more blocks selected from the group consisting of polyvinyl alcohol-based resin, polyethylene glycol, polypropylene glycol, polyvinyl propylene, and polyacrylamide. The inkjet ink composition according to item.   The inkjet ink composition according to any one of claims 1 to 5, wherein an average particle diameter of the resin particles is 100 nm or more and 1000 nm or less.   The inkjet ink composition according to any one of claims 1 to 6, further comprising a crosslinking agent.   The ink-jet ink composition according to claim 1, wherein the colorant contains a pigment and / or a dye.   The recording method which has the process of recording the inkjet ink composition as described in any one of Claims 1-8 on a recording medium.

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