JP2019178246A - Ink, ink jet printing method, ink cartridge, inkjet printer and colored fabric - Google Patents

Abstract

To provide a colored fabric excellent in color optical density, and excellent in continuous discharge property.SOLUTION: There is provided an ink comprising an aqueous dispersion of a polymer having a structure derived from a dye, and a water soluble organic solvent, the polymer is at least one kind selected from a group formed of an acrylic polymer, polyurethane and polyurea, the solubility of the polymer in the water soluble organic solvent is 0.05 mass% or greater, the water soluble organic solvent is ether or amide, the boiling point of the water soluble organic solvent is 287°C or greater. There are also provided an ink cartridge and an inkjet printer including the ink, an inkjet printing method using the ink, and a colored fabric including the fabric and the polymer.SELECTED DRAWING: None

Description

  The present invention relates to an ink, an ink jet textile printing method, an ink cartridge, an ink jet printer, and a colored cloth.

  An inkjet ink is an ink that can be applied to an inkjet method, and is widely used for various applications. For example, inkjet textile printing does not require the production of a plate, can quickly form an image with excellent gradation, and uses only a necessary amount of ink as a formed image, so that there is little waste liquid. It can be said that this is an excellent printing method having advantages.

  For example, Patent Document 1 discloses an ink containing a polymer having a structure derived from a dye.

Japanese Patent Application Laid-Open No. 10-226763

  However, as a result of studies by the present inventors, it has been found that the ink-jet printing using the ink described in Patent Document 1 has room for further improvement in terms of color density and continuous ejection properties.

  An object of the present invention is to provide a colored cloth excellent in color density and capable of providing an ink excellent in continuous discharge property, an ink jet textile printing method using the ink, an ink cartridge and an ink jet printer having the ink, and An object of the present invention is to provide a colored fabric having an excellent color density.

  The inventors of the present invention have made extensive studies and found that the above problems can be solved by the following means.

<1>
An ink containing an aqueous dispersion of a polymer having a structure derived from a dye and a water-soluble organic solvent,
The polymer is at least one selected from the group of acrylic polymer, polyurethane and polyurea;
The solubility of the polymer in the water-soluble organic solvent is 0.05% by mass or more,
The water-soluble organic solvent is ether or amide,
The ink, wherein the water-soluble organic solvent has a boiling point of 287 ° C or higher.
<2>
The ink according to <1>, wherein the content of the water-soluble organic solvent is 25 to 45% by mass with respect to the total mass of the ink.
<3>
The ink according to <1> or <2>, wherein the dye is at least one dye selected from the group consisting of oil-soluble dyes, disperse dyes, and vat dyes.

<4>
The dye is C.I. I. The ink according to any one of <1> to <3>, which is Solvent Black 3.
<5>
The ink according to any one of <1> to <4>, wherein the acid value of the polymer is from 5 to 90 mgKOH.
<6>
The ink according to any one of <1> to <5>, wherein the acid value of the polymer is 10 to 90 mgKOH.
<7>
The ink according to any one of <1> to <6>, wherein the polymer is at least one selected from the group of polyurethane and polyurea.
<8>
The ink according to <7>, wherein the polymer is a polyurea obtained by reacting a compound represented by the following general formula (M-3) with a compound having two or more isocyanate groups in one molecule. .

In general formula (M-3),
R ^{303 to} R ³¹⁸ each independently represent a hydrogen atom or an alkyl group.
R ^{319 to} R ³²⁰ each independently represents an alkyl group.
<9>
The ink according to any one of <1> to <8>, which is for inkjet.
<10>
<1>-<9> The inkjet textile printing method which has the process of printing the ink of any one of <9> on a fabric by an inkjet system.
<11>
The ink-jet printing method according to <10>, further comprising a heat treatment step.
<12>
An ink cartridge containing the ink according to any one of <1> to <9>.
<13>
<1>-<9> The inkjet printer containing the ink of any one of <9>.
<14>
A colored fabric comprising a fabric and a polymer,
The polymer has a structure derived from a dye,
A colored fabric, wherein the polymer is at least one selected from the group of acrylic polymers, polyurethanes, and polyureas.

The present inventors have found that the above problem can be solved by using an aqueous dispersion of a polymer having a structure derived from a dye and an ink containing a specific water-soluble organic solvent.
The use of a polymer having a structure derived from a dye in an ink is already known, but there is a problem that association between dye structures is likely to occur and a sufficient color density cannot be obtained.
By using a water-soluble organic solvent having a high solubility in the above polymer, the polymer having a structure derived from the dye is easily dissolved, and the dye skeleton that was originally associated is easily dissolved. In addition, by using a water-soluble organic solvent having a high boiling point (boiling point is 287 ° C. or higher), the volatilization rate of the water-soluble organic solvent at the time of heat fixing to a fabric in ink jet printing is lowered. Therefore, since the time for the polymer containing the structure derived from the dye and the water-soluble organic solvent to be increased increases, the polymer and the water-soluble organic solvent coexist until immediately before heat fixing to the fabric. Dye association is easily disengaged, and in heat fixing to fabric, the original color density of the dye can be sufficiently expressed, and the dye association is easily disengaged, so that the continuous discharge property of the ink containing the polymer is also improved. It can be improved.

  An object of the present invention is to provide a colored cloth having excellent color density and capable of providing an ink having excellent continuous ejection properties, an ink jet textile printing method using the ink, an ink cartridge and an ink jet printer having the ink, and a color developing A colored fabric having excellent density can be provided.

  Hereinafter, the present invention will be described in detail.

In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents at least one of acrylate and methacrylate, “(meth) acryl” represents at least one of acryl and methacryl, and “(meth) acryloyl” represents at least acryloyl and methacryloyl. Represents a kind.
In the present specification, the “substituent group A” refers to the substituent described in [0117] of International Publication No. 2017/131107.
In the present specification, the substituent group A1 includes the following substituents.

(Substituent group A1)
A halogen atom, an alkyl group (preferably 1 to 30 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms), a heterocyclic group (preferably 3 to 3 carbon atoms) 30), acyl groups (preferably having 2 to 30 carbon atoms), hydroxyl groups, carboxyl groups, sulfo groups, cyano groups, nitro groups, alkoxy groups (preferably having 1 to 30 carbon atoms), aryloxy groups (preferably having carbon numbers) 6-30), an acyloxy group (preferably having 2 to 30 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms), a carbamoyl group, a sulfamoyl group, An alkylsulfonyl group (preferably having 1 to 30 carbon atoms), an arylsulfonyl group (preferably having 6 to 30 carbon atoms), an amino group, an A substituent comprising a ruamino group (preferably having 1 to 30 carbon atoms), an alkylsulfonylamino group (preferably having 1 to 30 carbon atoms), an arylsulfonylamino group (preferably having 6 to 30 carbon atoms), or a combination of two or more thereof. Group.

(Polymer having structure derived from dye)
The ink of the present invention contains a polymer having a structure derived from a dye. In the polymer having a structure derived from a dye (hereinafter, also referred to as “dye polymer”) used in the present invention, the structure derived from a dye is one or more arbitrary hydrogen atoms removed from an organic compound used as a dye. A group formed by removing one or two arbitrary hydrogen atoms from an organic compound used as a dye.
The dye polymer is a pigment multimer including a structure derived from a dye, and may be a linear polymer or a network polymer.

  The method for obtaining the dye polymer is arbitrary, but a monomer containing a structure derived from a dye (also referred to as “dye monomer”) is polymerized or copolymerized with other monomers to obtain a dye polymer. Examples thereof include a method, or a method of preparing a polymer not having a structure derived from a dye in advance and then introducing a structure derived from the dye by a polymer reaction or the like to obtain a dye polymer. The method for producing the dye polymer or the polymer having no structure derived from the dye is not particularly limited, but those synthesized by radical polymerization, addition polymerization or condensation polymerization are preferably used.

  As the dye, a dye classified by a color index (abbreviated as “CI”), or a structure obtained by substituting an arbitrary substituent within the range in which the effect of the present invention is obtained, or the dye From the above, a structure in which an arbitrary substituent is removed within the range where the effects of the present invention are obtained is preferable.

  The dye is preferably at least one dye selected from the group consisting of oil-soluble dyes, disperse dyes, and vat dyes (hereinafter also referred to as “dyes” or “specific dyes”).

The specific dye in the present invention is not particularly limited, but the following dyes are particularly preferable. “CI” is an abbreviation for “color index”. Moreover, what is described as “Disperse” is a disperse dye, and what is described as “Solvent” is an oil-soluble dye.
C. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86,
C. I. Solvent Yellow 2, 14, 16, 21, 33, 43, 44, 56, 82, 85, 93, 98, 114, 131, 135, 157, 160, 163, 167, 176, 179, 185, 189,
C. I. Disperse Red 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240,
C. I. Solvent Red 8, 23, 24, 25, 49, 52, 109, 111, 119, 122, 124, 135, 146, 149, 150, 168, 169, 172, 179, 195, 196, 197, 207, 222, 227, 312, 313,
C. I. Disperse Blue 3, 5, 19, 26, 26: 1, 35, 55, 56, 58, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108, 131, 141 145, 359, 360,
C. I. Solvent Blue 3, 4, 5, 35, 36, 38, 44, 45, 59, 63, 67, 68, 70, 78, 83, 97, 101, 102, 104, 105, 111, 122,
C. I. Disperse Orange 1, 1: 1, 5, 7, 20, 23, 25, 25: 1, 33, 56, 76,
C. I. Solvent Orange 3, 14, 54, 60, 62, 63, 67, 86, 107,
C. I. Disperse Violet 8, 11, 17, 23, 26, 27, 28, 29, 36, 57,
C. I. Solvent Violet 8, 9, 11, 13, 14, 26, 28, 31, 36, 59,
C. I. Solvent Green 3, 5, 7, 28,
C. I. Disperse Brown 2,
C. I. Solvent Brown 53,
C. I. Solvent Black 3, 5, 7, 27, 29, 34
As the vat dye, the following dyes are particularly preferable.
C. I. Vat Yellow 2, 4, 10, 20, 33; I. Vat Orange 1, 2, 3, 5, 7, 9, 13, 15; I. Vat Red 1, 2, 10, 13, 15, 16, 41, 61; I. Vat Blue 1, 3, 4, 5, 6, 8, 12, 14, 18, 19, 20, 29, 35, 41; C.I. I. Vat Black 1, 8, 9, 13, 14, 20, 25, 27, 29, 36, 56, 57, 59, 60

  As described above, a method for obtaining a dye polymer is arbitrary, and examples thereof include a method of obtaining a dye polymer by polymerizing or copolymerizing a dye monomer with another monomer. In the case where the dye does not have a reactive group, a reactive group can be appropriately added to form a dye monomer.

The dye polymer of the present invention is at least one selected from the group of acrylic polymers, polyurethanes and polyureas.
The acrylic polymer is a polymer having at least one repeating unit in the group consisting of repeating units derived from (meth) acrylic acid and repeating units derived from (meth) acrylic acid ester.
Moreover, the styrene polymer in this invention means the polymer which has a repeating unit derived from styrene.
Further, the polyurethane (also referred to as “urethane polymer”) in the present invention is a polymer having a urethane bond.
The polyurethane may be a polymer further having a urea bond. A polymer having a urethane bond and a urea bond is also referred to as “polyurethane / urea”.
The polyurea (also referred to as “urea polymer”) in the present invention is a polymer having a urethane bond.
The polyurea may further be a polymer having a urethane bond. A polymer having a urethane bond and a urea bond is also referred to as “polyurethane / urea”.

The dye polymer of the present invention is preferably a polymer having a structure represented by the following general formula (M-1).
The polymer having the structure represented by the general formula (M-1) (also referred to as “polymer (1)”) will be described.

In general formula (M-1), R < ¹⁰¹ > -R < ¹²⁰ > represents a hydrogen atom or a substituent each independently. At least one of R ^{101 to} R ¹²⁰ is bonded to the polymer through a single bond or a linking group.
Examples of the substituent include a substituent selected from the substituent group A (preferably a substituent selected from the substituent group A1).

The polymer (1) is not particularly limited as long as it has a structure represented by the general formula (M-1). The polymer (1) may be a linear polymer or a network polymer. As a form in which the polymer (1) has a structure represented by the general formula (M-1), at least one of R ^{101 to} R ^{120 in} the general formula (M-1) is a single bond or via a linking group. It is a form bonded to the polymer, for example, a form in which the structure represented by the general formula (M-1) is incorporated in the molecular chain constituting the polymer, The form which the side chain which has a structure represented by a formula (M-1) couple | bonded may be sufficient.
The polymer (1) is preferably a polymer having a repeating unit represented by the following general formula (1a), at least one of polyurea and polyurethane having a structure represented by the general formula (M-1), More preferably, it is at least one of polyurea and polyurethane having a structure represented by the general formula (M-1).

  The polymer (1) is at least one of polyurea and polyurethane obtained by reacting a compound represented by the following general formula (M-2) with a compound having two or more isocyanate groups in one molecule. It is preferable that

In General Formula (M-2), R ^{203 to} R ²²⁰ each independently represent a hydrogen atom or a substituent.
Examples of the substituent include a substituent selected from the substituent group A (preferably a substituent selected from the substituent group A1).

  The polymer (1) preferably has an anionic group. As the anionic group, an acid group is preferable, and a carboxyl group is more preferable. That is, the polymer (1) preferably has a carboxyl group.

Polymer (1) is
Polyurea (also referred to as “polyurea (3)”) obtained by reacting a compound represented by the general formula (M-3) with a compound having two or more isocyanate groups in one molecule;
A polyurethane (also referred to as “polyurethane (4)”) obtained by reacting a compound represented by the general formula (M-4) with a compound having two or more isocyanate groups in one molecule; and the general formula At least one of polyurethanes (also referred to as “polyurethane (5)”) obtained by reacting a compound represented by (M-5) with a compound having two or more isocyanate groups in one molecule. Preferably there is.

  Hereinafter, polyurea (3), polyurethane (4), and polyurethane (5), which are preferred examples of polymer (1), will be described in detail.

<Polyurea (polyurea (3)) obtained by reacting a compound represented by the general formula (M-3) with a compound having two or more isocyanate groups in one molecule>
Polyurea (3) is obtained by reacting a compound represented by the following general formula (M-3) with a compound having two or more isocyanate groups in one molecule.

In General Formula (M-3), R ^{303 to} R ³¹⁸ each independently represent a hydrogen atom or an alkyl group. R ^{319 to} R ³²⁰ each independently represents an alkyl group.

The compound represented by the general formula (M-3) used when synthesizing the polyurea (3) and the compound having two or more isocyanate groups in one molecule (also referred to as “polyisocyanate compound”) A monomer.
The polyurea (3) is a polymer having a urea bond, and is obtained by polymerizing a compound represented by the general formula (M-3) as a monomer and a polyisocyanate compound as a monomer.
Moreover, polyurea (3) may be obtained by reacting another monomer in addition to these.
Although the method for obtaining polyurea (3) is arbitrary, the method of superposing | polymerizing or copolymerizing the compound represented by general formula (M-3) and obtaining polyurea (3) is mentioned.

(Compound represented by formula (M-3))
The compound represented by formula (M-3) will be described.
In General Formula (M-3), the alkyl group in the case where R ^{303 to} R ³¹⁸ represent an alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group. R ^{303 to} R ³¹⁸ are preferably hydrogen atoms from the viewpoint of raw material availability.

The alkyl group of R ^{319 to} R ³²⁰ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
A compound in which R ^{303 to} R ³¹⁸ are hydrogen atoms and R ³¹⁹ and R ³²⁰ are methyl groups is also referred to as Solvent Black 3 (also known as Sudan Black B).

The alkyl group in the case where R ^{303 to} R ³¹⁸ represent an alkyl group, and the alkyl group of R ^{319 to} R ³²⁰ may further have a substituent. Examples of the further substituent include the above-mentioned substituent group A, preferably an alkoxy group (preferably a methoxy group) and the like.

  The content of the compound represented by the general formula (M-3) is preferably 15% by mass or more with respect to all monomers used when synthesizing the polyurea (3), and is preferably 15 to 80% by mass. % Is more preferable. Content of compound represented by general formula (M-3) used when synthesizing polyurea (3) (corresponding to the compound represented by general formula (M-3) in polyurea (3)) The higher the monomer unit content), the higher the density of the image obtained when printing with inkjet ink.

As a compound represented by the said general formula (M-3), the compound synthesize | combined by the well-known method can also be used, and a commercial item can be used.
Specific examples of the compound represented by the general formula (M-3) are shown below, but are not limited thereto.

  As described above, (M-3-1) is also referred to as Solvent Black 3 (also known as Sudan Black B).

(Polyisocyanate compound)
As a monomer used when synthesizing the polyurea (3), at least one polyisocyanate compound is used.
The polyisocyanate compound preferably includes a compound having two isocyanate groups in one molecule and a compound having three or more isocyanate groups in one molecule.

  Examples of the compound having two isocyanate groups in one molecule include phenylene diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane. Diisocyanate, bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate, lysine diisocyanate, a multimer of the above diisocyanate, and a reaction product of 1 mol of diol and 2 mol of diisocyanate can be used.

  The compound having 3 or more isocyanate groups in one molecule is preferably a compound having 3 to 5 isocyanate groups in one molecule.

  Although it does not specifically limit as a compound which has three isocyanate groups in 1 molecule, The compound represented by either of the following general formula (A)-(C) is preferable.

In general formula (A),
R _{1 to} R ₃ each independently represents an alkylene group, a cycloalkylene group, an arylene group, or a divalent linking group formed by combining two or more thereof.

  As an alkylene group, a C2-C8 alkylene group is mentioned, for example, A hexamethylene group and a trimethyl hexamethylene group are preferable.

Examples of the cycloalkylene group include a cycloalkylene group having 6 to 10 carbon atoms, and an isophoronyl group, a hydrogenated xylene group, and a hydrogenated tolyl group are preferable.
The general structures of isophoronyl group, hydrogenated xylene group, and hydrogenated tolyl group are shown below. The hydrogenated xylene group and hydrogenated tolyl group also include those in which double bonds remain partially unhydrogenated.

* Represents a bonding position.

  Examples of the arylene group include an arylene group having 6 to 8 carbon atoms, and a divalent group in which two hydrogen atoms are removed from xylene and a divalent group in which two hydrogen atoms are removed from toluene are preferable.

In general formula (B),
R _{4 to} R ₆ each independently represents an alkylene group, a cycloalkylene group, an arylene group, or a divalent linking group formed by combining two or more thereof.
R _{4 to} R ₆ have the same meanings as R _{1 to} R ₃ , respectively, and the same applies to the preferred range.

In general formula (C):
R _{7 to} R ₉ each independently represents an alkylene group, a cycloalkylene group, an arylene group, or a divalent linking group formed by combining two or more thereof.
R < ₇ > -R < ₉ > is synonymous with R < ₁ > -R < ₃ > respectively and is the same also about a preferable range.

  Specific examples of the compound represented by any one of the general formulas (A) to (C) are not particularly limited. For example, Takenate D-110N, D120N, D-127N, D-140N, D-160N, D-165N, D-170N, D-170NH, D-172N, D-177N (made by Mitsui Chemicals), Duranate 24A-100, 22A-75P, 21S-75E, TPA-100, TKA-100, MFA- 75B, MHG-80B, TLA-100, TSA-100, TSS-100, TSE-100, P301-75E, E402-80B, E405-70B, AE700-100 (manufactured by Asahi Kasei Corporation).

  As the polyisocyanate compound, polymeric MDI (manufactured by Wako Pure Chemical Industries, Ltd.) and death module (manufactured by Covestro) represented by the following general formula (D) can also be preferably used.

  A catalyst can be used in the reaction between the compound represented by the general formula (M-3) and the polyisocyanate compound. As the catalyst, a tin compound, a titanium compound, a bismuth compound, a zinc compound, an organic base (such as a tertiary amine compound or diazabicycloundecene (DBU)), or the like can be preferably used.

(Other monomers)
Polyurea (3) may be a polymer obtained by reacting other monomers other than these in addition to the compound represented by the above formula (M-3) and the polyisocyanate compound.
As other monomers, diol, triol or diamine is preferable. A diol having a carboxyl group or a triol having a carboxyl group is also preferred.

Polyurea (3) may be a polymer further having a urethane bond. A polymer having a urethane bond and a urea bond is also referred to as “polyurethane / urea”.
As one kind of preferred forms of the polyurea (3), a polymer (polyurethane obtained by further reacting polyurethane with polyurea obtained by reacting the compound represented by the general formula (M-3) with the polyisocyanate compound. / Urea).

(Structure of polyurea (3))
Polyurea (3) is preferably introduced with a dispersing group from the viewpoint of dispersibility in water. The dispersing group may be ionic or nonionic. The molecular structure of polyurea (3) may be either linear or branched.
The polyurea (3) preferably has a crosslinked structure. By having a crosslinked structure, the strength of the film formed by fusing the polyurea (3) is improved, and a colored cloth having excellent durability can be obtained. The crosslinked structure represents a structure obtained by using a compound having a total of three or more hydroxyl groups and isocyanate groups in the molecule as at least one monomer. Examples of the compound having three or more hydroxyl groups in the molecule include glycerin, polyglycerin, trimethylolpropane, pentaerythritol and the like. Examples of the compound having three or more isocyanate groups in the molecule include the above-described polymeric MDI, duranate (trade name, manufactured by Asahi Kasei Corporation) and the like.

The polyurea (3) may have a structure having an ionic group as a dispersing group. The introduction amount of the structure having an ionic group in the polyurea (3) is preferably introduced so that the acid value or amine value of the polyurea (3) is 1 to 60 mgKOH / g, and 1 to 30 mgKOH / g More preferably, it is introduced. Within the above range, the dispersion stability and washing fastness of the aqueous dispersion of polyurea (3) are excellent. The acid value or amine value can be determined by a neutralization titration method such as JIS (Japanese Industrial Standard) K 0070.
The polyurea (3) may have a structure having a nonionic group as a dispersing group. The introduction amount of the structure (monomer unit) having a nonionic group as a dispersing group is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass. Within the above range, the dispersion stability and washing fastness of the aqueous dispersion of polyurea (3) are excellent.
The polyurea (3) preferably has an anionic group.
As the anionic group, an acid group is preferable, and a carboxyl group is more preferable. That is, it is preferable that polyurea (3) has a carboxyl group.

<Polyurethane (polyurethane (4)) obtained by reacting a compound represented by formula (M-4) with a compound having two or more isocyanate groups in one molecule>
The polyurethane (4) may be a linear polymer or a network polymer.
The compound represented by the general formula (M-4) used when synthesizing the polyurethane (4) and the compound having two or more isocyanate groups in one molecule (also referred to as “polyisocyanate compound”) are: It is a monomer.
The polyurethane (4) is a polymer having a urethane bond, and is obtained by polymerizing a compound represented by the general formula (M-4) as a monomer and a polyisocyanate compound as a monomer.
The polyurethane (4) may be obtained by further reacting with another monomer in addition to these.
Although the method for obtaining a polyurethane (4) is arbitrary, the method of superposing | polymerizing or copolymerizing the compound represented by general formula (M-4) and obtaining a polyurethane (4) is mentioned.

  The content of the compound represented by the general formula (M-4) is preferably 15% by mass or more with respect to all monomers used when the polyurethane (4) is synthesized, and is 15 to 80% by mass. It is more preferable that Content of compound represented by general formula (M-4) used when synthesizing polyurethane (4) (monomer unit corresponding to compound represented by general formula (M-4) in polyurethane (4)) The greater the content, the higher the density of the image that can be obtained when the ink-jet ink is printed.

<Compound represented by formula (M-4)>
The compound represented by formula (M-4) will be described.

In General Formula (M-4), L ¹⁰¹ and L ¹⁰² each independently represent a divalent linking group. R ^{403 to} R ⁴¹⁸ each independently represents a hydrogen atom or a substituent.

  The compound represented by the general formula (M-4) is a pigment and can be used as a dye.

In the general formula (M-4), the divalent linking group represented by L ¹⁰¹ and L ¹⁰² is preferably an alkylene group, specifically, a methylene group, an ethylene group, a propylene group, or the like, preferably methylene. It is a group.

In General Formula (M-4), examples of the substituent in the case where R ^{403 to} R ⁴¹⁸ represent a substituent include a substituent selected from the aforementioned substituent group A, and preferably an alkyl group (more preferably 1 to 10 carbon atoms), a halogen atom (more preferably a chlorine atom), an amino group which may have a substituent, a sulfamoyl group which may have a substituent, a carbamoyl group which may have a substituent, An alkoxy group (more preferably having 1 to 10 carbon atoms) or an alkoxycarbonyl group (more preferably having 1 to 10 carbon atoms). When the amino group, sulfamoyl group or carbamoyl group has a substituent, the substituent is preferably an alkyl group (more preferably having 1 to 10 carbon atoms).

R ^{403 to} R ⁴¹⁸ preferably each independently represent a hydrogen atom, an alkyl group, a dialkylsulfamoyl group, a dialkylamino group, or a halogen atom.
More preferably, R ^{403 to} R ⁴¹⁸ each independently represent a hydrogen atom, a methyl group, a dibutylsulfamoyl group, a dipropylsulfamoyl group, a diethylamino group, or a chlorine atom. More preferably, R ^{403 to} R ⁴¹⁸ each independently represent a hydrogen atom or a methyl group.
It is particularly preferable that L ¹⁰¹ and L ¹⁰² in the general formula (M-4) represent a methylene group, and R ^{403 to} R ⁴⁰⁷ each represent a hydrogen atom.

  The compound represented by the general formula (M-4) can be synthesized, for example, by the following reaction mechanism.

In the general formulas (M-4-1A), (M-4-1B), (M-4-1AB), and (M-4-1C), L ¹⁰¹ , L ¹⁰² , R ^{403 to} R ⁴¹⁸ are each among the general formula ^(M-4), it has the same meaning as ^{L 101, L 102, R 403} ~R 418 preferred ranges are also the same.

From the compound represented by general formula (M-4-1A) and the compound represented by general formula (M-4-1B) in the above reaction mechanism, it is represented by general formula (M-4-1AB). The reaction for synthesizing the compound can be performed, for example, in accordance with Step 3 of Example 1 of International Publication No. 2016/096085.
From the compound represented by the general formula (M-4-1AB) in the reaction mechanism and the compound represented by the general formula (M-4-1C), a compound represented by the general formula (M-4) is obtained. The synthesis reaction can be performed, for example, according to Part B of page 8 of US Patent Application Publication No. 2015/0065697.
The compound represented by the general formula (M-4-1C) can be synthesized, for example, according to Example 1 of US Pat. No. 6,348,592.
Moreover, the compound represented by general formula (M-4-1A) and the compound represented by general formula (M-4-1B) are compoundable by a well-known method.

  Specific examples of the compound represented by the general formula (M-4-1A) are shown below, but are not limited thereto. In the structural formulas of the specific examples below, R represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group.

  Specific examples of the compound represented by the general formula (M-4-1B) are shown below, but are not limited thereto.

  Specific examples of the compound represented by the general formula (M-4-1C) are shown below, but are not limited thereto.

  Specific examples of the compound represented by the general formula (M-4) include specific examples of the compound represented by the general formula (M-4-1A) and the general formula (M-4-1B). And any combination of specific examples of the compound represented by the above general formula (M-4-1C). Although the specific example of a compound represented by general formula (M-4) below is shown, it is not limited to these.

(Polyisocyanate compound)
The polyisocyanate compound will be described.
As a monomer used when synthesizing the polyurethane (4), it is preferable to use at least one compound (diisocyanate) having two isocyanate groups in one molecule as a polyisocyanate compound.
The polyisocyanate compound is not particularly limited. (Isocyanatomethyl) cyclohexane, norbornene diisocyanate, lysine diisocyanate, a polymer of the above diisocyanate, and a reaction product of 1 mol of diol and 2 mol of diisocyanate can be used. These may be used alone or in combination.

  A catalyst can be used in the reaction between the compound represented by formula (M-4) and the polyisocyanate compound. As the catalyst, a tin compound, a titanium compound, a bismuth compound, a zinc compound, an organic base (such as a tertiary amine compound or diazabicycloundecene (DBU)), or the like can be preferably used.

(Other monomers)
Polyurethane (4) may be a polymer obtained by reacting other monomers in addition to the compound represented by formula (M-4) and the polyisocyanate compound.
As other monomers, diol, triol or diamine is preferable. A diol having a carboxyl group or a triol having a carboxyl group is also preferred.

The polyurethane (4) may have a urea bond in the molecule. A polymer having a urethane bond and a urea bond is also referred to as “polyurethane / urea”.
Polyurethane (4) is obtained by reacting another polyurethane with the polyurethane obtained by reacting the compound represented by formula (M-4) with a compound having two or more isocyanate groups in one molecule. The resulting polyurethane / urea is preferred.

(Structure of polyurethane (4))
The polyurethane (4) preferably has a dispersing group from the viewpoint of dispersibility in water. The dispersing group may be ionic or nonionic. The molecular structure of the polyurethane (4) may be either linear or branched.
The polyurethane (4) preferably has a crosslinked structure from the viewpoint of fastness. By having a crosslinked structure, the strength of the film formed by fusing the polyurethane (4) in the heat treatment step during ink jet printing is improved, and a colored cloth having excellent durability can be obtained. The crosslinked structure represents a structure obtained by using a compound having a total of three or more hydroxyl groups and isocyanate groups in the molecule as at least one monomer. Examples of the compound having three or more hydroxyl groups in the molecule include glycerin, polyglycerin, trimethylolpropane, pentaerythritol and the like. Examples of the compound having three or more isocyanate groups in the molecule include polymeric MDI (trade name, manufactured by Tosoh Corporation), duranate (trade name, manufactured by Asahi Kasei Corporation), and the like.

The polyurethane (4) may have a structure having an ionic group as a dispersing group. The introduction amount of the structure having an ionic group in the polyurethane (4) is preferably introduced so that the acid value or amine value of the polyurethane (4) is 1 to 60 mgKOH / g, and 1 to 30 mgKOH / g More preferably, it is introduced. Within the above range, the dispersion stability and wash fastness of the aqueous dispersion of polyurethane (4) are excellent. The acid value or amine value can be determined by a neutralization titration method such as JIS (Japanese Industrial Standard) K 0070.
The polyurethane (4) may have a structure having a nonionic group as a dispersing group. The introduction amount of the structure (monomer unit) having a nonionic group as a dispersing group is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass. Within the above range, the dispersion stability and wash fastness of the aqueous dispersion of polyurethane (4) are excellent.
The polyurethane (4) preferably has an anionic group.
As the anionic group, an acid group is preferable, and a carboxyl group is more preferable. That is, the polyurethane (4) preferably has a carboxyl group.

<Polyurethane (polyurethane (5)) obtained by reacting a compound represented by formula (M-5) with a compound having two or more isocyanate groups in one molecule>
The polyurethane (5) may be a linear polymer or a network polymer.
The compound represented by the general formula (M-5) used when synthesizing the polyurethane (5) and the compound having two or more isocyanate groups in one molecule (also referred to as “polyisocyanate compound”) are: It is a monomer.
The polyurethane (5) is a polymer having a urethane bond, and is obtained by polymerizing a compound represented by the general formula (M-5) as a monomer and a polyisocyanate compound as a monomer.
The polyurethane (5) may be obtained by reacting another monomer in addition to these.

  Although the method for obtaining a polyurethane (5) is arbitrary, the method of superposing | polymerizing or copolymerizing the compound represented by general formula (M-5) and obtaining a polyurethane (5) is mentioned.

  The content of the compound represented by the general formula (M-5) is preferably 15% by mass or more with respect to all monomers used when the polyurethane (5) is synthesized, and is 15 to 80% by mass. It is more preferable that Content of compound represented by general formula (M-5) used when synthesizing polyurethane (5) (monomer unit corresponding to compound represented by general formula (M-5) in polyurethane (5)) The greater the content, the higher the density of the image that can be obtained when the ink-jet ink is printed.

<Compound represented by formula (M-5)>
The compound represented by formula (M-5) will be described.

In the general formula ^{(M-5), R 503} ~R 518 each independently represent a hydrogen atom or a substituent. However, at least one of R ^{508 to} R ⁵¹⁸ represents a group represented by any one of the following general formulas (R-1) to (R-9). R ⁵¹⁹ and R ⁵²⁰ each independently represents an alkyl group which may have a substituent. However, the compound represented by the general formula (M-5) has two or more hydroxyl groups.

In General Formula (R-1), L ¹ and L ² each independently represent a divalent linking group.
In General Formula (R-2), L ³ represents a divalent linking group, and R ²¹ represents a hydrogen atom or an alkyl group.
In General Formula (R-3), L ⁴ and L ⁵ each independently represent a divalent linking group.
In General Formula (R-4), L ⁶ represents a divalent linking group, and R ²² represents a hydrogen atom or an alkyl group.
In General Formula (R-5), L ⁷ and L ⁸ each independently represent a divalent linking group.
In General Formula (R-6), L ⁹ represents a divalent linking group, and R ²³ represents a hydrogen atom or an alkyl group.
In General Formula (R-7), L ¹⁰ represents a divalent linking group.
In the general formula ^(R-9), R ²⁴ represents an alkyl group. * Represents a bonding position.

  The compound represented by the general formula (M-5) is a pigment and can be used as a dye.

In general formula (M-5), R ^{503 to} R ⁵¹⁸ each independently represents a hydrogen atom or a substituent. At least one of R ^{508 to} R ⁵¹⁸ represents a group represented by any one of the general formulas (R-1) to (R-9).
The substituent in the case where R ^{503 to} R ⁵¹⁸ represent a substituent other than the group represented by any one of the above general formulas (R-1) to (R-9) is selected from the aforementioned substituent group A. Preferably, an alkyl group (more preferably 1 to 10 carbon atoms), an alkylamino group (more preferably 1 to 10 carbon atoms), a halogen atom (more preferably a chlorine atom, a bromine atom), An alkoxy group (more preferably having 1 to 10 carbon atoms) or an alkoxycarbonyl group (more preferably having 1 to 10 carbon atoms).

It is preferable that R ^{508 to} R ⁵¹⁸ each independently represent a group represented by any one of the general formulas (R-1) to (R-9) or a hydrogen atom.

R ⁵¹⁹ and R ⁵²⁰ each independently represents an alkyl group which may have a substituent.
R ⁵¹⁹ and R ⁵²⁰ may each independently represent an alkyl group having no substituent, or may represent an alkyl group having a substituent.
As an alkyl group which ^R519 and ^R520 represent, a C1-C5 alkyl group is preferable and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group are preferable.
If R ⁵¹⁹ and ^{R 520} represents an alkyl group having a substituent, a hydroxyl group is preferred as a substituent.

Note that at least one of R ^{508 to} R ⁵¹⁸ represents a group represented by any of the above general formulas (R-1) to (R-9).

In the general formula (R-1), the divalent linking group represented by L ¹ and L ² is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, specifically a methylene group or ethylene. Group, a propylene group, etc. are mentioned, Preferably it is an ethylene group.

In the general formula (R-2), the divalent linking group represented by L ³ is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, specifically, a methylene group, an ethylene group, or propylene. Group etc. are mentioned, Preferably it is an ethylene group.
In the general formula (R-2), the alkyl group represented by R ^21, preferably an alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group are preferable.

In the general formula (R-3), the divalent linking group represented by L ⁴ and L ⁵ is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, specifically, a methylene group, ethylene Group, a propylene group, etc. are mentioned, Preferably it is an ethylene group.

In the general formula (R-4), the divalent linking group represented by L ⁶ is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, specifically a methylene group, an ethylene group, or propylene. Group etc. are mentioned, Preferably it is an ethylene group.
In general formula (R-4), the alkyl group represented by R ²² is preferably an alkyl group having 1 to 5 carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group.

In the general formula (R-5), the divalent linking group represented by L ⁷ and L ⁸ is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, specifically, a methylene group, ethylene Group, a propylene group, etc. are mentioned, Preferably it is an ethylene group.

In the general formula (R-6), the divalent linking group represented by L ⁹ is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, specifically a methylene group, an ethylene group, or propylene. Group etc. are mentioned, Preferably it is an ethylene group.
In the general formula (R-6), the alkyl group represented by R ^23, preferably an alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group are preferable.

In the general formula (R-7), the divalent linking group represented by L ¹⁰ is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, specifically a methylene group, an ethylene group, or propylene. A methylene group and an ethylene group are preferable.

In the general formula (R-9), the alkyl group represented by R ^24, preferably an alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group are preferable.

Of R ^{8 to} R ¹⁸ , at least one of R ¹¹ , R ¹² , R ¹⁵ , R ¹⁶ and R ¹⁷ is represented by any one of the above general formulas (R-1) to (R-9). It is preferable to have a group, and at least one of R ¹¹ , R ¹⁵ , R ¹⁶ and R ¹⁷ further has a group represented by any one of the general formulas (R-1) to (R-9). preferable.

R ^{503 to} R ⁵⁰⁷ in the general formula (M-5) are preferably hydrogen atoms.

  The compound represented by the general formula (M-5) has two or more hydroxyl groups.

  The compound represented by the general formula (M-5) can be synthesized according to a known method.

  For example, when a compound represented by the general formula (M-5) is synthesized, a general formula (M) containing a group represented by any one of the general formulas (R-1) to (R-9) is previously prepared. The compound represented by -5-1A) and the compound represented by the general formula (M-5-1B) are respectively synthesized, and then azo-coupled to represent the compound represented by the general formula (M-5). A method of synthesizing a compound, specifically, a method of synthesizing by the following route A can be mentioned.

In the general formulas (M-5-1A), (M-5-1B), (M-5-1AB), and (M-5-1C), R ^{503 to} R ⁵¹⁸ are each represented by the general formula (M-1 ), The same as R ^{503 to} R ⁵¹⁸ , and the preferred range is also the same.
At least one of R ^{514 to} R ⁵¹⁸ represents a group represented by any of the above general formulas (R-1) to (R-9).

The compound represented by the general formula (M-5-1A) and the compound represented by the general formula (M-5-1AB) can be synthesized with reference to WO2016 / 096085 page 28 Examples. A commercial item can be used for general formula (M-5-1B).
The compound represented by the general formula (M-5-1C) can be synthesized, for example, according to Example 1 of US Pat. No. 6,348,592.
In addition, the step of coupling the compound represented by the general formula (M-5-1AB) and the compound represented by the general formula (M-5-1C) is described in US Patent Application Publication No. 2015/0065697. This can be done according to Part B on page 8.

In the route A, when at least one of R ^{514 to} R ^{518 in} the general formula (M-5-1A) represents a group represented by any one of the general formulas (R-1) to (R-9) In the case where at least one of R ^{508 to} R ^{513 in} the general formula (M-5-1B) represents a group represented by any one of the above general formulas (R-1) to (R-9) Or at least one of R ^{503 to} R ^{507 in} the general formula (M-5-1C) represents a group represented by any one of the above general formulas (R-1) to (R-9) Similarly, a compound represented by formula (M-5) can be synthesized.

The compound represented by the general formula (M-5) is represented by any one of the above general formulas (R-1) to (R-9) after azo coupling in advance, separately from the route A. The method of introduce | transducing group to be made, the method of specifically synthesize | combining by route B is mentioned.
“Route B” will be described below using the synthesis of compound (M-5-1) described below as an example.

  In this case, commercially available compounds (M-5-1A ′) and (M-5-1B ′) can be used. In addition, the step of coupling the compound (M-5-1AB ′) and the compound (M-5-1C ′) can be performed according to Part B of page 8 of US Patent Application Publication No. 2015/0065697. it can. The final amidation can be chlorinated by a known method, for example, the method of Experimental Chemistry Course 14 III, page 1799 and amidated by the method of Experimental Chemistry Course 14 III, page 1803.

  Specific examples of the compound represented by the general formula (M-5-1A) are shown below, but are not limited thereto. In the structural formulas of the following specific examples, R is Me (methyl group), Et (ethyl group), n-Pr (n-propyl group), i-Pr (isopropyl group), n-Bu (n-butyl group). Or i-Bu (isobutyl group).

In the compound represented by the general formula (M-5-1A), at least one of R ^{514 to} R ⁵¹⁸ represents a group represented by any one of the general formulas (R-1) to (R-9). Concrete example

None of R ^{514 to} R ⁵¹⁸ is a group represented by the general formula (M-5-1A), which is not a group represented by any one of the general formulas (R-1) to (R-9). Concrete example

  Specific examples of the compound represented by the general formula (M-1B) are shown below, but are not limited thereto. R is Me (methyl group), Et (ethyl group), n-Pr (n-propyl group), i-Pr (isopropyl group), n-Bu (n-butyl group), or i-Bu (isobutyl group). ).

Of the compound represented by the general formula (M-5-1B) in which at least one of R ^{508 to} R ⁵¹³ represents a group represented by any one of the above general formulas (R-1) to (R-9) Concrete example

None of R ^{508 to} R ⁵¹³ is a group represented by the general formula (M-5-1B), which is not a group represented by any one of the general formulas (R-1) to (R-9). Concrete example

Specific examples of the compound represented by the general formula (M-5-1C) are shown below, but are not limited thereto. R _A each independently represents an alkyl group (preferably Me (methyl group), Et (ethyl group), n-Pr (n-propyl group), i-Pr (isopropyl group), n-Bu (n-butyl). Group), i-Bu (isobutyl group), n-Pn (n-pentyl group), or i-Pn (isopentyl group)), a hydroxyalkyl group (preferably a hydroxymethyl group, a hydroxyethyl group, or a hydroxypropyl group) Represents.

  Specific examples of the compound represented by the general formula (M-5) include specific examples of the compound represented by the general formula (M-5-1A) and the general formula (M-5-1B). And any combination of specific examples of the compound represented by the general formula (M-5-1C). Although the specific example of a compound represented by general formula (M-5) below is shown, it is not limited to these.

(Polyisocyanate compound)
The polyisocyanate compound will be described.
As a monomer used when synthesizing the polyurethane (5), it is preferable to use at least one compound (diisocyanate) having two isocyanate groups in one molecule as a polyisocyanate compound.
The polyisocyanate compound is not particularly limited. (Isocyanatomethyl) cyclohexane, norbornene diisocyanate, lysine diisocyanate, a polymer of the above diisocyanate, and a reaction product of 1 mol of diol and 2 mol of diisocyanate can be used. These may be used alone or in combination.

  A catalyst can be used in the reaction of the compound represented by formula (M-5) and the polyisocyanate compound. As the catalyst, a tin compound, a titanium compound, a bismuth compound, a zinc compound, an organic base (such as a tertiary amine compound or diazabicycloundecene (DBU)), or the like can be preferably used.

(Other monomers)
The polyurethane (5) may be a polymer obtained by reacting other monomers in addition to the compound represented by the general formula (M-5) and the polyisocyanate compound.
As other monomers, diol, triol or diamine is preferable. A diol having a carboxyl group or a triol having a carboxyl group is also preferred.

The polyurethane (5) may have a urea bond in the molecule. A polymer having a urethane bond and a urea bond is also referred to as “polyurethane / urea”.
Polyurethane (5) is obtained by reacting (polymerizing) a compound represented by the general formula (M-5) with a compound having two or more isocyanate groups in one molecule. A polyurethane / urea obtained by reaction is preferred.

(Structure of polyurethane (5))
The polyurethane (5) preferably has a dispersing group from the viewpoint of dispersibility in water. The dispersing group may be ionic or nonionic. The molecular structure of the polyurethane (5) may be either linear or branched.
The polyurethane (5) preferably has a crosslinked structure. By having a crosslinked structure, the strength of the film formed by fusing the polyurethane (5) in the heat treatment step during ink jet printing is improved, and a colored cloth having excellent durability can be obtained. The crosslinked structure represents a structure obtained by using a compound having a total of three or more hydroxyl groups and isocyanate groups in the molecule as at least one monomer. Examples of the compound having three or more hydroxyl groups in the molecule include glycerin, polyglycerin, trimethylolpropane, pentaerythritol and the like. Examples of the compound having three or more isocyanate groups in the molecule include polymeric MDI (trade name, manufactured by Tosoh Corporation), duranate (trade name, manufactured by Asahi Kasei Corporation), and the like.

The polyurethane (5) may have a structure having an ionic group as a dispersing group. The introduction amount of the structure having an ionic group in the polyurethane (5) is preferably introduced so that the acid value or amine value of the polyurethane (5) is 1 to 60 mgKOH / g, and 1 to 30 mgKOH / g More preferably, it is introduced. Within the above range, the dispersion stability and wash fastness of the aqueous dispersion of polyurethane (5) are excellent. The acid value or amine value can be determined by a neutralization titration method such as JIS (Japanese Industrial Standard) K 0070.
The polyurethane (5) may have a structure having a nonionic group as a dispersing group. The introduction amount of the structure (monomer unit) having a nonionic group as a dispersing group is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass. Within the above range, the dispersion stability and wash fastness of the aqueous dispersion of polyurethane (5) are excellent.
The polyurethane (5) preferably has an anionic group.
As the anionic group, an acid group is preferable, and a carboxyl group is more preferable. That is, the polyurethane (5) preferably has a carboxyl group.

<Polymer having a repeating unit represented by the general formula (1a)>
The polymer (1) is also preferably a polymer having a repeating unit represented by the following general formula (1a) (also referred to as “polymer (1a)”).

In General Formula (1a), X ^1a represents a linking group, L ^1a represents a single bond or a divalent linking group, and D ^1a represents an arbitrary hydrogen atom from the structure represented by General Formula (M-1). Represents a dye residue removed.

In general formula (1a), X ^1a represents a linking group. X ^1a is preferably a linking group formed by polymerization, and preferably a portion corresponding to the main chain formed by the polymerization reaction. That is, X ^1a is preferably a partial structure of the polymer main chain. ^Examples of X ^1a include a linking group formed by polymerizing a substituted or unsubstituted unsaturated ethylene group, a linking group formed by ring-opening polymerization of a cyclic ether, and preferably a polymerized unsaturated ethylene group. A linking group formed as described above.
Specific examples of the repeating unit represented by the general formula (1a) include a (meth) acrylate repeating unit, a styrene repeating unit, a maleate repeating unit, a maleimide repeating unit, a vinyl ether repeating unit, and a cycloolefin repeating unit. A meth) acrylate repeating unit is preferred.
Although the preferable specific example of the repeating unit represented by General formula (1a) is shown below, it is not limited to these. The following Ra represents a hydrogen atom or a substituent (preferably a methyl group).

(Molecular weight of polymer (1a))
In the present invention, since the polymer (1a) is used in a state of being dispersed in water, the polymer (1a) has an optimum molecular weight range in terms of dispersibility. Is hard to get up. On the other hand, it is difficult to dissolve in water and an aqueous organic solvent as long as it is at least the lower limit of the optimum molecular weight range. Although it varies depending on the type of polymer (1a) used, it is generally preferable to use a polymer having a weight average molecular weight (Mw) of 2,000 to 2,000,000, preferably 2,000 to 1,000,000. More preferably, 3,000 to 80,000 are used, more preferably 3,000 to 30,000, particularly preferably 3,000 to 15,000. Is most preferred. The dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and particularly preferably 1.0 to 2.0. Mn represents a number average molecular weight.
The weight average molecular weight of the polymer (1a) can be calculated from gel permeation chromatography (GPC) measurement. In this specification, unless otherwise specified, GPC is measured using HLC-8220GPC (manufactured by Tosoh Corporation), and the column is measured with TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation), and the number average molecular weight. Was calculated by polystyrene conversion. The carrier may be selected as appropriate, but NMP (N-methylpyrrolidone) was used as long as it was soluble.

(Structure of polymer (1a))
The polymer (1a) has only to have the structure represented by the general formula (M-1) as an essential structure, but from the viewpoint of dispersibility in water, a hydrophobic group (electrically neutral It is more preferable to introduce a repeating unit containing at least one of a polar group having a low affinity with water and an ionic group (an electrically ionic polar group having a high affinity with water). preferable. The molecular structure of the polymer (1a) may be either linear or branched, may be random, alternating, periodic, or block, and may be a graft polymer designed with a trunk and branch structure.
As a method for forming the polymer (1a), a method such as so-called copolymerization is preferable from the viewpoint of design flexibility. Examples of the copolymer component include the following hydrophobic group-containing monomers, anionic group-containing monomers, cationic group-containing monomers, and other functional monomers.

  The content of the repeating unit having the structure represented by the general formula (M-1) in the polymer (1a) with respect to all repeating units is preferably 10 to 90% by mass, more preferably 25 to 90% by mass. Especially preferably, it is 50-90 mass%. If the content rate of the repeating unit which has a structure represented by general formula (M-1) is 10 mass% or more, the coloring power per unit mass will improve and the dyeing density to a fabric will become high. Moreover, it is easy to adjust molecular weight to an appropriate range at the time of a polymer (1a) synthesis | combination as it is 90 mass% or less.

(Hydrophobic group-containing monomer)
Examples of the hydrophobic group-containing monomer include vinyl monomers such as styrene monomers, phenyl group-containing (meth) acrylates, (meth) acrylic acid alkyl esters, alkyl vinyl ethers, (meth) acrylonitrile; Urethane group-containing vinyl monomer formed from polyisocyanate and polyol or polyamine; epoxy group-containing vinyl monomer formed from epichlorohydrin and bisphenol; polyvalent carboxylic acid and polyalcohol etc. are formed from monomers Ester group-containing vinyl monomers; silicone group-containing vinyl monomers formed from organopolysiloxanes and the like.
The polymer (1a) preferably contains a repeating unit derived from a monomer represented by the following general formula (AC) from the viewpoint of familiarity with fibers, that is, the softness of the polymer (1a).

In General Formula (AC), R ^1AC represents a hydrogen atom or a methyl group. If R ^1AC represents a hydrogen ^{atom, R 2AC} may have a substituent, a linear or branched alkyl group or a cycloalkyl ^{group, if R 1AC} represents methyl ^{group, R 2AC} is an aliphatic group A linear or branched alkyl group or cycloalkyl group which may have a substituent having 3 or more nucleus atoms.

  The number of nuclear atoms represents the number of atoms other than hydrogen atoms.

When R ^1AC represents a hydrogen atom, R ^2AC is preferably a linear or branched alkyl group, more preferably a linear alkyl group. When R ^2AC has a substituent, the substituent preferably does not contain an aromatic ring, and is preferably a hydroxyl group or an alkoxyl group.
When R ^1AC represents a methyl group, R ^2AC is preferably an unsubstituted linear or branched alkyl group, more preferably a linear alkyl group. When R ^2AC has a substituent, the substituent preferably does not contain an aromatic ring, and is preferably a hydroxyl group or an alkoxyl group.

Specific examples of the monomer represented by the general formula (AC) include acrylic monomers (R ^1AC = hydrogen atom): methyl acrylate, ethyl acrylate, propyl acrylate, iso-propyl acrylate, butyl acrylate, tert- Butyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate homopolymer, iso-octyl acrylate, lauryl acrylate, tetradecyl acrylate, hexadecyl acrylate, stearyl acrylate, Benzyl acrylate, vinyl acetate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, ethoxyethyl acrylate, ethoxydiethyleneglycol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, carboxyethyl acrylate; methacrylic monomer (R ^{1AC =} methyl): methyl methacrylate, iso -Propyl methacrylate homopolymer, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, isoamyl acrylate, hexyl methacrylate, cyclohexyl acrylate, octyl acrylate, iso-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate homopolymer, lauryl methacrylate , Tetradecyl methacrylate, hexadecyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate homopolymer, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, ethoxy And ethyl methacrylate, methoxy methacrylate, and carboxyethyl methacrylate.

  The content of the repeating unit derived from the monomer represented by the general formula (AC) in the polymer (1a) with respect to all repeating units is preferably 5 to 90% by mass, more preferably 5 to 50% by mass. It is particularly preferably 10 to 30% by mass. If the content of the repeating unit derived from the monomer represented by the general formula (AC) is 5% by mass or more, the polymer (1a) as a particle is melted in the heat treatment process at the time of printing and the fiber is coated. The friction resistance can be improved. Moreover, it is easy to control an average particle diameter as it is 90 mass% or less.

  Next, the ionic group includes an anionic group and a cationic group. Examples of monomers that give these ionic groups include the following.

(Cationic group-containing monomer)
As the cationic group-containing monomer, the following unsaturated amine-containing monomer, unsaturated ammonium salt-containing monomer, and the like can be used. Examples of the unsaturated amine-containing monomer include vinylamine, allylamine, vinylpyridine, methylvinylpyridine, N, N-dialkylaminostyrene, N, N-dialkylaminoalkyl (meth) acrylate, and dialkylaminoethyl vinyl ether. It is done.
Examples of the unsaturated ammonium salt-containing monomer include those obtained by quaternizing the unsaturated tertiary amine-containing monomer with a quaternizing agent.

(Anionic group-containing monomer)
As an anionic group-containing monomer, a monomer containing -COOM (M represents a hydrogen atom or a counter cation), an unsaturated sulfonic acid monomer, an unsaturated phosphoric acid monomer, or an anhydride thereof And a monomer containing -COOM is preferable. -COOM represents a carboxyl group (when M represents a hydrogen atom) or a salt thereof (when M represents a counter cation). When M represents a counter cation, ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are listed. Lithium ion, sodium ion, potassium ion and ammonium ion are preferable, and lithium ion or sodium ion is more preferable.
Examples of the monomer containing —COOM include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, carboxyethyl acrylate, and the like. Among these, (meth) acrylic acid is preferable.
Examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, sulfuric acid ester of 2-hydroxyalkyl (meth) acrylate, or salts thereof. Is mentioned.
Examples of the unsaturated phosphoric acid monomer include vinylphosphonic acid, phosphoric acid ester of hydroxyalkyl (meth) acrylate (having 2 to 6 carbon atoms), and (meth) acrylic acid alkylphosphonic acid.

The polymer (1a) preferably has a repeating unit containing -COOM.
A repeating unit containing -COOM can be introduced into the polymer (1a) using a monomer containing -COOM.
The content of the repeating unit containing -COOM in the polymer (1a) with respect to all repeating units is preferably 5 to 90% by mass, more preferably 5 to 50% by mass, and particularly preferably 5 to 20% by mass. is there. If the content rate of the repeating unit containing a carboxyl group or its salt is 5 mass% or more, the dispersibility of the polymer (1a) in the ink can be improved. Moreover, it is easy to control an average particle diameter as it is 90 mass% or less.

[Other functional monomers]
In addition to the above copolymerization method, for example, urethane polymerization of a urethane-forming group-containing monomer into which an ionic group has been introduced in advance, or epoxy polymerization of an epoxy-forming group-containing monomer into which an ionic group has been introduced in advance. This method can also be adopted. In addition, the polymer (1a) can be obtained by introducing a target ionic group after polymerizing the basic polymer. In addition, other components may be contained, for example, polyethylene oxide having a hydroxyl group or an amide group, polyol or hydroxyalkyl ester-containing monomer, acrylamide, hydroxyalkyl acrylate, vinyl acetate without ionicity. , Vinyl alcohol, N-ethylmethacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone and the like can be copolymerized as monomers.

  The polymer (1a) has at least one structure each represented by the general formula (M-1), a repeating unit derived from the monomer represented by the general formula (AC), and a repeating unit containing -COOM. Preferably, the monomer having a structure represented by the general formula (M-1), the monomer represented by the general formula (AC), and the monomer containing -COOM are copolymerized. It is preferable that it is a polymer obtained by this.

  Polymer (1a) is a copolymer of (meth) acrylate, alkyl (meth) acrylate or aromatic (meth) acrylate having a structure represented by general formula (M-1), and (meth) acrylic acid (salt) Coalescence is preferred.

  The dye polymer of the present invention is preferably at least one selected from the group consisting of polyurethane and polyurea.

The acid value of the dye polymer is preferably 5 to 90 mgKOH / g, more preferably 10 to 90 mgKOH / g, still more preferably 10 to 80 mgKOH / g, and 15 to 70 mgKOH / g. Particularly preferred.
If the acid value is 5 mgKOH / g or more, when the dye polymer is used as a dispersion, the dispersibility of the dispersion can be maintained, and the stability of the ink does not decrease, which is preferable. On the other hand, if the acid value is 90 mgKOH / g or less, the hydrophilicity of the ink film of the dispersion of the dye polymer after heat fixing is not high, and the dyeing fastness such as washing resistance and sweat resistance is not deteriorated, which is preferable. .

The acid value can be measured according to the indicator titration method of JIS K 1557. However, the neutralizing agent used to neutralize acidic groups is removed and measured. For example, when organic amines are used as a neutralizing agent, a dye polymer aqueous dispersion or dye polymer is applied to a glass plate and dried at a temperature of 60 ° C. under a reduced pressure of 20 mmHg for 24 hours. Is volatilized and the resulting coating film is dissolved in N-methylpyrrolidone, and the acid value can be measured according to the indicator titration method of JIS K 1557.
Note that 760 mmHg = 101325 Pa.

<Aqueous dispersion of dye polymer>
The aqueous dispersion of the dye polymer contains at least water and the dye polymer, and the dye polymer is dispersed in water. The aqueous dispersion of the dye polymer may contain an aqueous organic solvent. Further, depending on the method for producing the aqueous dispersion of the dye polymer, either a low molecular surfactant or a high molecular dispersant may be used together or not (so-called self-dispersing).
In the dye polymer aqueous dispersion, only one dye polymer can be used, or two or more dye polymers can be mixed and used in an arbitrary ratio.

In an aqueous dispersion of a dye polymer, the dye polymer is used in a state of being dispersed in water, not in a state of being dissolved in water.
In the state where the dye polymer is dispersed in water, unlike the state in which the dye polymer is dissolved in water, the polymer is substantially insoluble in water, and thus is excellent in terms of water resistance such as washing resistance and sweat resistance. In the ink-jet printing method of the present invention, a step of washing with water after printing is unnecessary, and therefore the dye polymer is a polymer that is substantially insoluble in water. In the aqueous dispersion of the dye polymer, the dye polymer that is not soluble in water is dispersed as particles, and the average particle diameter is preferably 50 to 500 nm. When the dye polymer is dissolved in water, the dye polymer is not present as particles in water.
It is preferable to use ultrapure water as water.

  When dispersed in water, the dye polymer is easily compatible with water (easy to get wet) and electrostatic repulsion (repulsive force) as a property of the dye polymer itself or by adsorption with the low molecular surfactant or polymer dispersant used in combination. ) Or steric repulsion prevents re-aggregation of the fine particles of the dye polymer, and has a function of suppressing sedimentation.

The dye polymer is in the form of particles in the aqueous dispersion. The average particle diameter of the particulate dye polymer in the aqueous dispersion of the dye polymer is preferably 50 to 500 nm, more preferably 50 to 300 nm, and particularly preferably 50 to 200 nm. Within this range, the fabric can be printed by the ink jet method.
As the average particle size in the present specification, the value of the volume average size (MV) measured using a particle size distribution measuring device (Nanotrack UPA EX150, trade name, manufactured by Nikkiso Co., Ltd.) was used.

The content of the dye polymer contained in the aqueous dispersion of the dye polymer is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass. Within this range, a high-density colored cloth can be obtained in printing while ensuring storage stability as an inkjet ink.
The content of water contained in the aqueous dispersion of the dye polymer is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. Within this range, the aqueous dispersion of the dye polymer can be stored stably, and discharge stability as an inkjet ink can be imparted, which is preferable. In addition, that the aqueous dispersion of the dye polymer can be stored stably indicates that precipitation or the like is unlikely to occur.

(Low molecular surfactant or polymer dispersant)
The low molecular surfactant or the high molecular dispersant is preferably a low molecular surfactant or a high molecular dispersant having a hydrophobic group and an ionic group, and is added when the dye polymer is dispersed. The low molecular surfactant or polymer dispersant adsorbs to the surface of the dye polymer and blends (wet) it with water, and the dye polymer fine particles ground by mechanical action are electrostatically repulsive (repulsive) or steric repulsive. This prevents the re-aggregation of fine particles and has a function of suppressing sedimentation.

  The content of the low-molecular surfactant is preferably in the range of 0.001 to 5.0% by mass with respect to the total mass of the dye polymer aqueous dispersion, and the surface tension of the aqueous dispersion is within this range. It is preferable to adjust arbitrarily.

  The content of the polymeric dispersant is preferably in the range of 0.001 to 50% by mass with respect to the total mass of the dye polymer aqueous dispersion, and the surface tension of the aqueous dispersion can be arbitrarily set within such a range. It is preferable to adjust.

(Method for producing aqueous dispersion of dye polymer)
Although the manufacturing method of the aqueous dispersion of dye polymer is not specifically limited, For example, the method shown to the following (i)-(iv) is mentioned.
(I) After mixing a dye polymer powder or paste and, if necessary, an aqueous organic solvent, a low molecular surfactant or a polymer dispersant in water, glass beads, zirconia beads, titania beads, or A method of finely dispersing with an attritor or a mill with stainless steel balls,
(Ii) The dye polymer is synthesized in an organic solvent, or the dye polymer taken out in a solid state after being synthesized in an organic solvent is dissolved in the organic solvent, and water, optionally a neutralizer, an emulsifier (surfactant), and A method of adding an organic solvent and, when an organic solvent is added, appropriately removing the organic solvent to obtain an aqueous dispersion of the dye polymer,
(Iii) An organic solvent, a compound represented by the general formula (M-2) described later, a polyisocyanate compound, and other monomers and a polymerization initiator as necessary are added in the organic solvent. The compound represented by the general formula (M-2) is polymerized and added with water, optionally a neutralizing agent, an emulsifier (surfactant) and a chain extender to emulsify the polymer, and the polymer is chain-extended. A method of obtaining an aqueous dispersion of a dye polymer by removing the solvent,
(Iv) A solution obtained by reacting the compound represented by formula (M-2) with a polyisocyanate compound, in which a first prepolymer having an isocyanate group at a terminal is dissolved in an organic solvent, a dispersible structure A solution in which the second prepolymer having an isocyanate group at the end is dissolved in an organic solvent, optionally mixing an emulsifier (surfactant) and the organic solvent, and water, optionally an emulsifier (surfactant). Method of adding and emulsifying and removing an organic solvent as appropriate to obtain an aqueous dispersion of a dye polymer

  In addition, a nonionic surfactant or an anionic surfactant can be added as a dispersion aid to the aqueous dispersion of the dye polymer, but these surfactants have a dispersion stability. It is preferable to add a small amount so as not to decrease.

<Ink>
The ink of the present invention contains at least an aqueous dispersion of a dye polymer. That is, the ink of the present invention is a dispersion liquid in which a dye polymer is dispersed in a liquid containing water. In addition, the dye polymer is in the form of particles in the ink, and the preferred average particle diameter of the particulate dye polymer is the same as that described above.

  The content of the dye polymer in the ink of the present invention is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and more preferably 1 to 10% by mass.

  The water content in the ink of the present invention is preferably 30 to 90% by mass, and more preferably 40 to 85% by mass.

  The ink of the present invention is preferably used for inkjet. That is, the ink of the present invention is preferably an inkjet ink.

(Water-soluble organic solvent)
The ink of the present invention contains a water-soluble organic solvent. The solubility of the dye polymer in the water-soluble organic solvent is 0.05% by mass or more.
The water-soluble organic solvent is ether or amide. The boiling point of the water-soluble organic solvent is 287 ° C. or higher.

The water-soluble organic solvent preferably has a solubility in water at 25 ° C. of 10 g / 100 g-H ₂ O or more, more preferably 20 g / 100 g-H ₂ O or more, and in any proportion with water. Those that are miscible are particularly preferred.

  When the solubility of the dye polymer in the water-soluble organic solvent is 0.05% by mass or more, the color density can be improved, which is preferable. When the solubility is 0.05% by mass or more, the color density can be dramatically improved in heat fixing after printing on a fabric by an ink jet method.

  This is a phenomenon that cannot be seen with ordinary textile dye inks and pigment inks. In the present invention, the water-soluble organic solvent is likely to dissolve the polymer containing the dye, and the dye skeleton that was originally associated with it is It is thought that it was easy to be solved and the color development inherent to the dye was fully expressed.

  The solubility of the dye polymer in the water-soluble organic solvent is preferably 5% by mass or less, and more preferably 1% by mass or less.

The solubility can be measured by a general method, but in the present invention, it can be measured by the following method. The polymer aqueous dispersion containing the dye is naturally left on a petri dish at 25 ° C. and dried until there is no decrease in mass. 100 g of a water-soluble organic solvent is weighed in a glass vial, and the polymer solid containing the dye obtained above is added thereto, and then 30 minutes with an ultrasonic cleaner (manufactured by ASONE, 1-6900-01). Apply ultrasonic waves and visually evaluate the presence or absence of dissolution. The solubility (mass%) is calculated from the weight of the maximum amount of solid that dissolves completely and the mass of the water-soluble organic solvent, where appropriate, by changing the weight of the dye polymer solid.

  As described above, when the boiling point of the water-soluble organic solvent is 287 ° C. or higher, the color density can be improved. On the other hand, when the boiling point is lower than 287 ° C., a sufficient color density may not be obtained. is there. This is presumably because the higher the boiling point, the lower the volatilization rate of the water-soluble organic solvent at the time of heat fixing, and the longer the time for the polymer containing the dye and the water-soluble organic solvent to become familiar. Moreover, although it is estimated that the higher boiling point is that the drying on the ink jet nozzle surface is suppressed, the continuous discharge property can be greatly improved.

In the present invention, the boiling point can be measured by a general distillation method under atmospheric pressure. The boiling point in the specification is the value of the boiling point under standard conditions (1 atm, 25 ° C.).
1 atmosphere = 101.325 kPa.

  In the measurement of the boiling point of the water-soluble organic solvent, when the boiling point exceeds 350 ° C., the water-soluble organic solvent may be decomposed during the measurement, and it may be difficult to measure the exact boiling point. In the present invention, a water-soluble organic solvent having a boiling point higher than 350 ° C. can be used with a boiling point of “350 ° C. or higher”.

The content of the water-soluble organic solvent is preferably 25 to 45% by mass and more preferably 30 to 40% by mass with respect to the total mass of the ink.
When the content of the water-soluble organic solvent is 25% by mass or more with respect to the total mass of the ink, the dye polymer is easily dissolved, and the inkjet nozzle surface is difficult to dry. It is preferable that the property is not deteriorated. The content of the water-soluble organic solvent is preferably 45% by mass or less with respect to the total mass of the ink because the storage stability of the polymer containing the dye in the ink is hardly deteriorated. The content of the water-soluble organic solvent is preferably appropriately selected within the above range.

  The water-soluble organic solvent is not particularly limited as long as it satisfies the above. Specifically, triethylene glycol, tetraethylene glycol, polyethylene glycol (for example, molecular weight 400 to 800), hydroxyethylpyrrolidone, hydroxy Propyl pyrrolidone, valerolactam, caprolactam, etc. are mentioned, but from the viewpoint of dischargeability in the ink jet method and easiness of volatilization during heat fixing, triethylene glycol, tetraethylene glycol, polyethylene glycol 400, hydrohydroxyethyl pyrrolidone, hydroxy Propyl pyrrolidone and the like are more preferable, triethylene glycol, tetraethylene glycol and hydrohydroxyethyl pyrrolidone are particularly preferable, triethylene glycol and tetraethylene glycol. The most preferred.

(Crosslinking agent)
When the ink of the present invention is used for textile printing, the ink of the present invention may contain a crosslinking agent for the purpose of improving the friction resistance or the fastness to washing of the colored cloth. Examples of the crosslinking agent include blocked isocyanate crosslinking agents (for example, Meikanate CX, TP-10, DM-35HC, SU-268A, etc., all manufactured by Meisei Kogyo Co., Ltd., trade names) and polyfunctional epoxy crosslinking agents (for example, , Denacor EX-313, 314, 322, 411, etc., all manufactured by Nagase ChemteX Corporation, trade names).

(PH adjuster)
The ink of the present invention can use a pH adjusting agent for the purpose of adjusting the pH. As a pH adjuster, neutralizers, such as an organic base and an inorganic alkali, can be used, for example. When the ink of the present invention is used for inkjet, the storage stability of the ink can be improved by adjusting the pH of the ink. The pH adjuster is preferably added so that the pH of the ink is 5 to 12, and more preferably added so that the pH is 5 to 9.

(Other ingredients)
The ink of the present invention may contain other components other than those described above. Examples of other components include colorants other than dye polymers, organic solvents, surfactants, optical brighteners, surface tension modifiers, antifoaming agents, anti-drying agents, lubricants, thickeners, UV absorbers. , Anti-fading agents, antistatic agents, matting agents, antioxidants, specific resistance adjusting agents, rust inhibitors, inorganic pigments, anti-reducing agents, antiseptics, antifungal agents, chelating agents, and the like. As these components, those described in International Publication No. 2017/131107 can be preferably used.

When the ink of the present invention is used for inkjet (inkjet ink), the surface tension of the ink is preferably adjusted to 20 mN / m to 70 mN / m, and more preferably adjusted to 25 mN / m to 60 mN / m. preferable. Further, when the ink is used for inkjet, the viscosity of the ink is preferably adjusted to 40 mPa · s or less, more preferably adjusted to 30 mPa · s or less, and particularly preferably adjusted to 20 mPa · s or less. preferable. The viscosity is measured by controlling the temperature at 25 ° C. using an E-type rotational viscometer.
Surface tension and viscosity are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant, a surfactant and the like.

  The method for preparing the ink of the present invention is not particularly limited. For example, the ink can be prepared by mixing an aqueous dispersion of a dye polymer and, if necessary, water or other components.

The ink (preferably inkjet ink) of the present invention is preferably used for textile printing.
The ink of the present invention is more preferably used for inkjet printing in which a fabric is printed by an inkjet method.

[Inkjet printing method]
The ink jet textile printing method of the present invention is an ink jet textile printing method having a step of printing on a fabric by an ink jet method using the ink of the present invention (preferably an ink jet ink). Preferred embodiments include the following two embodiments.
1st aspect: The inkjet textile printing method which has the process of printing directly on a fabric by the inkjet system using the ink of this invention.
Second aspect: A pretreatment step in which an aqueous pretreatment liquid containing an aggregating agent is applied to a fabric to obtain a pretreated fabric, and a fabric pretreated by an ink jet method using the ink of the present invention is directly marked. An inkjet printing method having a printing process.
In the present invention, “direct printing” on a fabric by an ink jet method does not require a transfer step, and does not require a step of directly printing ink on a fabric and applying a printing paste. Is both directly printed on the fabric.
The ink jet textile printing method of the present invention produces the effects of excellent quality (texture) of colored cloth, image sharpness and fastness to dry friction with simple workability without producing waste materials such as waste water and transfer paper.

(Pretreatment process)
The pretreatment step in the second aspect is a step of obtaining a pretreated fabric by applying an aqueous pretreatment liquid containing a flocculant to the fabric. The method for applying the aqueous pretreatment liquid to the fabric is not particularly limited, and examples thereof include a coating method, a padding method, an ink jet method, a spray method, and a screen printing method.
The flocculant contained in the aqueous pretreatment liquid is not particularly limited as long as it has an action of aggregating the dye polymer, but is at least one selected from organic acids, polyvalent metal salts, and cationic compounds. It is preferable.
In particular, when the aggregating agent is a cationic compound or a polyvalent metal salt and the dye polymer has an anionic group (preferably an acid group, more preferably a carboxyl group), printing is performed by the inkjet printing method. Highly colored fabric can be obtained. This is because the pre-treated cationic compound or polyvalent metal salt stays on the fabric surface as a result of agglomeration at the moment of contact with the ink containing the polyurethane having an anionic group, so that it exists on the surface. It is considered that the amount of dye polymer to be increased was increased and the concentration could be increased. More preferably, the flocculant is a cationic compound.

≪Polyvalent metal salt≫
The polyvalent metal salt is a compound composed of a divalent or higher valent metal ion and an anion. Specifically, calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium hydroxide, calcium carbonate, magnesium chloride, magnesium acetate, magnesium sulfate, magnesium carbonate, barium sulfate, barium chloride, zinc sulfide, zinc carbonate, copper nitrate Etc.

≪Cationic compound≫
The cationic compound is not particularly limited, and may be a low molecular compound or a high molecular compound.
Examples of the low molecular weight cationic compound include (2-hydroxyethyl) trimethylammonium chloride, benzoylcholine chloride, benzyltriethylammonium chloride, trimethylacetohydrazide ammonium chloride, 1-butyl-1-methylpyrrolidinium chloride, 3- Examples thereof include hydroxy-4- (trimethylammonio) butyrate hydrochloride, glycidyltrimethylammonium chloride, L-carnitine hydrochloride and the like.
Examples of the high molecular weight cationic compound include water-soluble and positively active in water such as polyallylamine or a derivative thereof, an amine-epihalohydrin copolymer, or other quaternary ammonium salt type cationic polymer. Examples include charged cationic polymers. In some cases, a water-dispersible cationic polymer can also be used.

A flocculant may be used individually by 1 type and may be used together 2 or more types.
The aqueous pretreatment liquid may contain, for example, a surfactant, a resin and the like in addition to water and an aqueous organic solvent.

  The ink-jet printing method of the present invention is further integrated with the fiber by fusing the dye polymer to the fiber of the fabric by adding a heat treatment step, thereby further improving the friction resistance without impairing the texture. There is an advantage that it can be granted.

(Heat treatment process)
The ink jet textile printing method of the present invention preferably further includes a heat treatment step. In particular, by performing a heat treatment step after printing on the fabric, the dye polymer particles can be melted (or softened), and the adhesion to the fibers can be improved (that is, heat-treated for melt dyeing). be able to). The colored fabric is preferably dried and then subjected to heat treatment for the purpose of melting and dyeing, usually at 100 to 250 ° C., more preferably 100 to 200 ° C., particularly preferably 120 to 200 ° C. The heat treatment time is preferably 30 seconds to 3 minutes.

(Post-processing)
The fabric colored by the inkjet printing method of the present invention (colored fabric) is excellent in the flexibility and fastness (friction resistance) of the texture, but if necessary, the entire surface is padded with a post-treatment agent. Thus, it is possible to obtain a colored fabric with improved texture flexibility and fastness (particularly friction resistance).

(Fabric)
Examples of fabrics to which the inkjet printing method of the present invention can be applied include the following. Examples of the fabric (fiber type) include synthetic fibers such as nylon, polyester, and acrylonitrile, semi-synthetic fibers such as acetate and rayon, natural fibers such as cotton, silk, and wool, and mixed fibers, woven fabrics, knitted fabrics, and non-woven fabrics. Can be mentioned.
As the fabric, a pretreated fabric can also be used. The pretreatment liquid can be applied by a coating method, a padding method, an ink jet method, a spray method, a screen printing method, or the like. The pretreatment liquid contains an aggregating agent that aggregates the polymer (1), and is preferably an aqueous solution. Examples of the flocculant include organic acids, polyvalent metal salts, and cationic compounds.
Apparel includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses and the like. It is also suitable for bedding, handkerchiefs, cushion covers, curtains and the like.

[Ink cartridge and inkjet printer]
The present invention also relates to an ink cartridge having the ink of the present invention (preferably inkjet ink) and an ink jet printer having the ink of the present invention (preferably inkjet ink).

[Colored fabric]
The present invention is a colored fabric comprising a fabric and a polymer,
The polymer has a structure derived from a dye,
It also relates to a colored fabric, wherein the polymer is at least one selected from the group of acrylic polymers, polyurethanes and polyureas.
The fabric and the polymer (dye polymer) are as described above.

[Method for producing colored fabric]
The ink of the present invention (preferably inkjet ink) can also be used in a method for producing a colored fabric having a step of printing on a fabric by an inkjet method. The preferred range of the process for printing on the fabric by the ink jet method is the same as described above. The manufacturing method of the colored fabric may also include the above-described pretreatment process. Moreover, it is preferable to have the above-mentioned heat processing process also about the manufacturing method of a colored cloth.

  Hereinafter, the present invention will be described in more detail based on examples. However, the scope of the present invention is not limited to the examples shown below.

Example 1
(Preparation of Prepolymer 1 in tetrahydrofuran (THF) solution)
In a three-neck flask, 400 g of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), C.I. I. Solvent Black 3 (manufactured by Wako Pure Chemical Industries, Ltd.) 125 g, THF 100 g, Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) 18.75 g were added and stirred at 65 ° C. for 8 hours. By high performance liquid chromatography, C.I. I. The disappearance of Solvent Black 3 was confirmed. This solution was reprecipitated with 3,500 mL of hexane, and the prepolymer 1 was collected by filtration.
(High-performance liquid chromatography measurement conditions)
Apparatus: SHIMADZU Nexera X2 (manufactured by Shimadzu Corporation)
Column: TSKgel ODS-120H (manufactured by Tosoh Corporation)
Eluent: Liquid A) 1 L of water, 1 mL of trifluoroacetic acid
B liquid) 1L of tetrahydrofuran, 1mL of trifluoroacetic acid
Changed from A solution concentration 60% and B solution concentration 40% to A solution concentration 0% and B solution concentration 100% over 6 minutes, and then kept A solution concentration 0% and B solution concentration 100% for 2 minutes. .

(Preparation of aqueous dispersion of dye polymer (1))
In a three-necked flask, 6.35 g of caprolactone diol (Aldrich), 3.97 g of 2,2-bis (hydroxymethyl) butyric acid (Tokyo Kasei), 0.54 g of trimethylolpropane (Tokyo Kasei) In addition, 13.07 g of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 56 g of THF, and 0.072 g of Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) were added and stirred at 65 ° C. for 4 hours.
3.24 g of the obtained liquid, Prepolymer 1 (5.28 g), 12.32 g of THF, 10.42 g of ethyl acetate and 0.102 g of triethylamine were put in a homogenizer, and further 35.63 g of ultrapure water, sodium dodecyl sulfate (Tokyo) 11.72 g (made by Kasei Co., Ltd.) was added, stirred at 16,000 rpm for 12 minutes, and passed through a 1 μm filter to obtain an emulsion.
Thereafter, 1.8 g of a 10 mass% aqueous solution of the above emulsion and UCAT SA102 (trade name, manufactured by San Apro Co., Ltd.) was added to the three-necked flask, and pure water was added so that the solid content concentration was 20 mass%. , Kept at 50 ° C. for 2 days for reaction. Thereafter, coarse particles were removed by 1 μm filter filtration to obtain 45 g of an aqueous dispersion (1) (20% by mass) of a dye polymer. The acid value of the dye polymer in the aqueous dispersion (1) of the dye polymer was 10 mgKOH.

<Preparation of ink composition (1)>
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered with a 0.8 μm filter (manufactured by Advantech) to obtain an ink composition (1).
Aqueous dispersion of dye polymer (1) (dispersed solid content 20% by mass), 50 parts by mass Water-soluble organic solvent: triethylene glycol (TEG) (manufactured by Tokyo Chemical Industry Co., Ltd.), 35 parts by mass Olfin E1010 (day Shinshin Chemical Co., Ltd.) 1 part by weight Water, 14 parts by weight

(Inkjet printing)
The ink composition (1) is filled in an ink cartridge, and an ink jet printer (manufactured by Seiko Epson Corporation, PX-045A) is used in advance to prepare 60% by mass of a 5% by mass aqueous solution of Katiomaster PD-7 (manufactured by Yokkaichi Gosei Co., Ltd.). A solid image was printed on cotton broad (D5005, manufactured by Akabori Sangyo Co., Ltd.) soaked and dried at 25 ° C. for 12 hours. Printing was performed by appropriately overlapping as necessary so that the total amount of ink to be ejected was about 30 g / m ² . After drying at 25 ° C. for 12 hours, using a heat press (AF-54TEN, manufactured by Asahi Textile Machinery Co., Ltd.), heat fixing treatment is performed at a temperature of 200 ° C., a pressure of 0.20 N / cm ^{2 for} a time of 60 seconds, Obtained.

Example 2
An ink composition (2) was obtained in the same manner as in Example 1, except that the water-soluble organic solvent was changed to tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.).
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (2) to obtain a colored fabric.

Example 3
An ink composition (3) was obtained in the same manner as in Example 1 except that the water-soluble organic solvent was changed to polyethylene glycol 400 (PEG400) (manufactured by Tokyo Chemical Industry Co., Ltd.).
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (3) to obtain a colored fabric.

Example 4
An ink composition (4) was obtained in the same manner as in Example 1, except that the water-soluble organic solvent was changed to hydroxylethylpyrrolidone (HEP) (manufactured by Tokyo Chemical Industry Co., Ltd.).
In addition, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (4) to obtain a colored fabric.

Example 5
An ink composition (5) was obtained in the same manner as in Example 1, except that the water-soluble organic solvent was changed to 25 parts by mass of tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.).
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (5) to obtain a colored fabric.

Example 6
An ink composition (6) was obtained in the same manner as in Example 1, except that the water-soluble organic solvent was changed to 45 parts by mass of tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.).
In addition, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (6) to obtain a colored fabric.

Example 7
An aqueous dispersion (7) of a dye polymer was obtained in the same manner as in Example 1, except that the acid amount of the dye polymer in the aqueous dispersion (1) of the dye polymer was changed to 10 mgKOH to be 5 mgKOH. .
Example 1 except that the aqueous dispersion (1) of the dye polymer was changed to the aqueous dispersion (7) of the dye polymer and the water-soluble organic solvent was changed to tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.). Similarly, an ink composition (7) was obtained.
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (7) to obtain a colored fabric.

Example 8
An aqueous dispersion (8) of a dye polymer was obtained in the same manner as in Example 1 except that the composition amount was changed so that the acid value of 10 mgKOH of the dye polymer in the aqueous dispersion of dye polymer (1) was 90 mgKOH.
Example 1 except that the aqueous dispersion (1) of the dye polymer was changed to an aqueous dispersion (8) of the dye polymer, and the water-soluble organic solvent was changed to tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.). In the same manner, an ink composition (8) was obtained.
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (8) to obtain a colored fabric.

Example 9
An ink composition (9) was obtained in the same manner as in Example 1 except that the water-soluble organic solvent was changed to 15 parts by mass of tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.).
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (9) to obtain a colored fabric.

Example 10
An ink composition (10) was obtained in the same manner as in Example 1, except that the water-soluble organic solvent was changed to 49 parts by mass of tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.).
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (10) to obtain a colored fabric.

Example 11
An aqueous dispersion (11) of a dye polymer was obtained in the same manner as in Example 1, except that the composition amount was changed so that the acid value of 10 mgKOH of the dye polymer in the aqueous dispersion of dye polymer (1) was 100 mgKOH.
Example 1 except that the aqueous dispersion (1) of the dye polymer was changed to the aqueous dispersion (11) of the dye polymer and the water-soluble organic solvent was changed to tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.). Similarly, an ink composition (11) was obtained.
In addition, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (11) to obtain a colored fabric.

Example 12
C. I. Solvent Black 3 to C.I. I. A dye polymer aqueous dispersion (12) was obtained in the same manner as in Example 1 except that the composition was changed to Solvent Black 5 (manufactured by Tokyo Chemical Industry Co., Ltd.) and the composition amount was changed so that the acid value of the dye polymer was 10 mgKOH. It was.
Example 1 except that the aqueous dispersion (1) of the dye polymer was changed to the aqueous dispersion (12) of the dye polymer and the water-soluble organic solvent was changed to tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.). In the same manner, an ink composition (12) was obtained.
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (12) to obtain a colored fabric.

Example 13
C. I. Solvent Black 3 to C.I. I. Disperse Blue 359 (manufactured by Arimoto Chemical Co., Ltd.) was used, and the dye polymer aqueous dispersion (13) was prepared in the same manner as in Example 1 except that the composition amount was changed so that the acid value of the dye polymer was 10 mgKOH. Obtained.
Example 1 except that the aqueous dispersion (1) of the dye polymer was changed to the aqueous dispersion (13) of the dye polymer and the water-soluble organic solvent was changed to tetraethylene glycol (tetraEG) (manufactured by Tokyo Chemical Industry Co., Ltd.). Similarly, an ink composition (13) was obtained.
Further, ink-jet printing was carried out in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (13) to obtain a colored fabric.

Example 14
An ink was prepared in the same manner as in Example 2 except that the dye polymer aqueous dispersion (1) of Example 2 was changed to a dye polymer aqueous dispersion (D-1-A) prepared by the following method. A composition (14) was obtained.
Moreover, ink-jet printing was performed in the same manner as in Example 2 except that the ink composition (2) was changed to the ink composition (14) to obtain a colored fabric.

[Preparation of polymer (D-1-1)]
10 g of N-methylpyrrolidone (NMP) was added to a 100 mL three-necked flask, and the internal temperature was raised to 85 ° C. To this, 7.5 g of D-1, 2.0 g of 2-ethylhexyl methacrylate, 0.5 g of methacrylic acid, 0.16 g of V-601 (trade name, manufactured by Wako Pure Chemical Industries), and 0.55 g of 1-dodecanethiol A solution dissolved in 13.13 g of NMP was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was reacted at 85 ° C. for 1 hour, and then V-601 (0.16 g) was added, and further 1 hour later, V-601 (0.16 g) was added and reacted for 2 hours. The reaction solution is allowed to cool to 20 ° C., poured into 300 mL of hexane, crystals are precipitated, and the crystals are separated by filtration, and then dried for 1 day in a 60 ° C. blower dryer, and then the methacrylate polymer (D-1-1 ) The weight average molecular weight (Mw) in gel permeation chromatography (GPC) measurement was 7800 (polystyrene conversion).

[Preparation of aqueous dispersion of dye polymer (D-1-A)]
Add 3 g of methacrylate polymer (D-1-1), 10 g of zirconia beads (made by Nikkato, trade name YTZ ball, diameter 0.1 μm), 0.6 g of sodium oleate, and 11.4 g of ultrapure water. (Pulversette 7 manufactured by Fritsch) was used for dispersion for 10 hours at a rotation speed of 400 rpm (rotations per minute). From the obtained dispersion, zirconia beads were removed using a filter cloth to obtain an aqueous dispersion of a dye polymer (D-1-A, dispersion polymer concentration 20%).

Example 15
Except for changing the dye polymer aqueous dispersion (1) of Example 2 to the dye polymer aqueous dispersion (M-4-1-A) prepared by the following method, the same procedure as in Example 2 was performed. Ink composition (15) was obtained.
Moreover, ink-jet printing was performed in the same manner as in Example 2 except that the ink composition (2) was changed to the ink composition (15) to obtain a colored fabric.

[Synthesis of (M-4-1)]
Referring to US Pat. No. 6,348,592, 2,2-bis (hydroxymethyl) 2,3-dihydroperimidine, which is a raw material of (M-4-1), was synthesized. Further, 4-phenylazo-1-naphthylamine was synthesized with reference to International Publication No. 2016/096085.
In a three-necked flask, 24.7 g of 4-phenylazo-1-naphthylamine, 510 mL of acetic acid and 110 mL of propionic acid were added and stirred at 20 ° C. to dissolve. The concentrated hydrochloric acid 7.3mL was thrown into there and it cooled so that it might become 0-5 degreeC. While maintaining at 0 to 5 ° C., an 8.5% by mass aqueous solution of sodium nitrite was added dropwise and reacted for 1 hour after the addition to obtain a diazonium salt solution. In a three-necked flask, 23 g of 2,2-bis (hydroxymethyl) 2,3-dihydroperimidine and 150 mL of tetrahydrofuran (THF) were added and stirred at 20 ° C. to dissolve. This was cooled to 5 ° C. or lower, and the diazonium salt solution was added dropwise while maintaining the reaction temperature at 5 ° C. or lower, followed by stirring for 30 minutes to obtain a (MB-1) reaction solution. The precipitate was collected by filtration, washed with pure water until acetic acid ceased, and dried to obtain 40 g of (M-4-1) solid. When analyzed for (M-4-1), it was LC (Liquid Chromatography) -MS (Mass Spectrometry) (Nega) 487.2, (Posi) 489.1.

(Preparation of prepolymer (M-4-1-1) in tetrahydrofuran (THF) solution)
In a three-necked flask, 4.4 g of isophorone diisocyanate, 6.5 g of (M-4-1), 25.5 g of THF, 0.03 g of Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) and put at 65 ° C. Stir for 6 hours. The disappearance of (M-4-1) was confirmed by high performance liquid chromatography. THF was added so that the final solid content concentration was 30% by mass to obtain a THF solution of prepolymer M-4-1-1.
(High-performance liquid chromatography measurement conditions)
Apparatus: SHIMADZU Nexera X2 (manufactured by Shimadzu Corporation)
Column: TSKgel ODS-120H (manufactured by Tosoh Corporation)
Eluent: Liquid A) 1 L of water, 1 mL of trifluoroacetic acid
B liquid) 1L of tetrahydrofuran, 1mL of trifluoroacetic acid
Changed from A solution concentration 60% and B solution concentration 40% to A solution concentration 0% and B solution concentration 100% over 6 minutes, and then kept A solution concentration 0% and B solution concentration 100% for 2 minutes. .

(Preparation of aqueous dispersion of dye polymer (M-4-1-A))
In a container, 16.7 g of a THF solution of the prepolymer M-4-1-1 obtained above as the first prepolymer and Takenate D-116N (nonionic dispersion prepolymer, Mitsui Chemicals ( Co., Ltd.) 50% by mass of ethyl acetate solution 2.5g, ethyl acetate 11.3g, THF 0.8g was added. Furthermore, a mixed liquid of 35.6 g of pure water and 11.7 g of 4 mass% sodium dodecyl sulfate aqueous solution was added, stirred for 12 minutes at 16000 rpm, and emulsified to obtain an emulsion. Thereafter, the obtained emulsion was distilled off under reduced pressure to remove the organic solvent. Thereafter, 1.8 g of a 10% by mass aqueous solution of UCAT SA102 (trade name, manufactured by San Apro Co., Ltd.) was added to the emulsion, and pure water was added so that the solid content concentration was 20% by mass. The reaction was held for a day. Thereafter, coarse particles were removed by filtration to obtain 32 g of an aqueous dispersion of black polyurethane (M-4-1-A). The final solid content concentration of the polyurethane aqueous dispersion (M-4-1-A) was 20% by mass. The polyurethane contained in the aqueous polyurethane dispersion (M-4-1-A) was polyurethane / urea, and the average particle size (MV) was 105 nm.

Comparative Example 1
An ink composition (C1) was obtained in the same manner as in Example 1 except that the water-soluble organic solvent was changed to diethylene glycol (DEG) (manufactured by Tokyo Chemical Industry Co., Ltd.).
Moreover, ink-jet printing was performed in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (C1) to obtain a colored fabric.

Comparative Example 2
An ink composition (C2) was obtained in the same manner as in Example 1 except that the water-soluble organic solvent was changed to 2-pyrrolidone (2P) (manufactured by Tokyo Chemical Industry Co., Ltd.).
Also, a colored fabric was obtained by ink jet printing in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (C2).

Comparative Example 3
An ink composition (C3) was obtained in the same manner as in Example 1 except that the water-soluble organic solvent was changed to glycerin (Gly) (manufactured by Tokyo Chemical Industry Co., Ltd.).
Also, a colored cloth was obtained by ink jet printing in the same manner as in Example 1 except that the ink composition (1) was changed to the ink composition (C3).

  About the said Examples 1-15 and Comparative Examples 1-3, it evaluated as follows.

<Color density>
About the obtained colored cloth, color development density OD was measured using X-rite (X-rite company colorimeter, iPro1), and the following evaluation was implemented.
A: OD is 1.65 or more B: OD is 1.60 or more and less than 1.65 C: OD is 1.55 or more and less than 1.60 D: OD is less than 1.55 If C or more, it is practical No problem.

<Continuous discharge property>
About each ink composition, using the above-mentioned PX-045A, a 100% solid image of A4 size was printed on plain paper and repeatedly printed without cleaning, and each printed matter was visually evaluated.
A: Three or more A4 size solid images can be continuously printed without streaking or blurring.
B: Continuous printing of A4 size solid image with no streaking or blurring is 2 sheets or more and less than 3 sheets.
C: A continuous printing of A4 size solid images without streaking or blurring is 1 sheet or more and less than 2 sheets.
D: No streaking or blurring, and no A4 size solid image can be printed.
If it is C or more, there is no practical problem.

Table 1 shows the evaluation results of Examples 1 to 15 and Comparative Examples 1 to 3.
In the aqueous dispersion of the dye polymer, the dye nucleus of the dye polymer, the acid value (mg KOH / g), the solubility (mass%) of the water-soluble organic solvent, the boiling point (° C.), the structure, and the added amount (ink composition) Table 1 also shows the content of the water-soluble organic solvent relative to the total mass of (% by mass)).
Here, the acid value of the dye polymer is determined by applying the dye polymer to a glass plate, drying it at a temperature of 60 ° C. under a reduced pressure of 20 mmHg for 24 hours, and dissolving the obtained coating film in N-methylpyrrolidone. It is a value measured according to the indicator titration method of 1557.
As for the color density, the color density (OD value) was also described along with the evaluation.

In Table 1, SB3, SB5, and DB359 each represent the following.
SB3: C.I. I. Solvent Black 3
SB5: C.I. I. Solvent Black 5
DB359: C.I. I. Disperse Blue 359

  As is apparent from Table 1, it can be seen that the inks of the examples of the present invention have higher color density and excellent continuous discharge properties than the inks of the comparative examples.

Claims (14)

An ink containing an aqueous dispersion of a polymer having a structure derived from a dye and a water-soluble organic solvent,
The polymer is at least one selected from the group of acrylic polymer, polyurethane and polyurea;
The solubility of the polymer in the water-soluble organic solvent is 0.05% by mass or more,
The water-soluble organic solvent is ether or amide,
An ink, wherein the water-soluble organic solvent has a boiling point of 287 ° C or higher.   The ink according to claim 1, wherein the content of the water-soluble organic solvent is 25 to 45 mass% with respect to the total mass of the ink.   The ink according to claim 1 or 2, wherein the dye is at least one dye selected from the group consisting of oil-soluble dyes, disperse dyes, and vat dyes.   The dye is C.I. I. The ink according to any one of claims 1 to 3, which is Solvent Black 3.   The ink according to any one of claims 1 to 4, wherein the acid value of the polymer is 5 to 90 mgKOH.   The ink according to any one of claims 1 to 5, wherein the acid value of the polymer is 10 to 90 mgKOH.   The ink according to claim 1, wherein the polymer is at least one selected from the group of polyurethane and polyurea. The ink according to claim 7, wherein the polymer is a polyurea obtained by reacting a compound represented by the following general formula (M-3) with a compound having two or more isocyanate groups in one molecule. .

In general formula (M-3),
R ^{303 to} R ³¹⁸ each independently represent a hydrogen atom or an alkyl group.
R ^{319 to} R ³²⁰ each independently represents an alkyl group.   The ink according to any one of claims 1 to 8, which is for inkjet.   An inkjet printing method comprising a step of printing the ink according to any one of claims 1 to 9 on a fabric by an inkjet method.   The inkjet printing method according to claim 10, further comprising a heat treatment step.   An ink cartridge containing the ink according to claim 1.   An ink jet printer comprising the ink according to claim 1. A colored fabric comprising a fabric and a polymer,
The polymer has a structure derived from a dye;
A colored cloth, wherein the polymer is at least one selected from the group of acrylic polymers, polyurethanes, and polyureas.