JP2020002221A - Ink set, inkjet printing method, ink cartridge, and inkjet printer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set or the like capable of providing a colored cloth excellent in reflection density and image clarity. An ink set including an inkjet ink including an aqueous dispersion of an oil-soluble dye represented by a general formula (MA) and an inkjet ink including an aqueous dispersion of a pigment, and an inkjet using the ink set. A printing method, an ink cartridge having the above ink set, and an inkjet printer. In formula (MA), R1 to R20 each independently represent a hydrogen atom or a substituent. [Selection diagram] None

Description

  The present invention relates to an ink set, an inkjet printing method, an ink cartridge, and an inkjet printer.

  An inkjet ink is an ink applicable to an inkjet method, and is widely used for various uses. For example, ink-jet printing does not require the production of a printing plate, can quickly form an image with excellent gradation, and furthermore uses only a necessary amount of ink as a formed image, thereby reducing the amount of waste liquid. It can be said that this is an excellent printing method having advantages.

  In addition, conventionally, an ink containing a pigment or a dye as a coloring material has been known. Pigment inks containing a pigment as a coloring material are particularly preferably used for recording characters and the like, since they have low bleeding and good water resistance and light resistance. Dye inks containing a dye as a coloring material are particularly preferably used for recording images and the like, since they have good gloss and color developability and clear colors.

  When a pigment ink and a dye ink having the above characteristics are used in combination, the recording quality of both characters and images recorded on a recording medium is improved. For these reasons, ink sets provided with both pigment ink and dye ink have been widely used in recent years.

  For example, Patent Literature 1 discloses that a first ink containing water, a first metal ion as a pigment and a counter ion of a pigment, and a second metal as a counter ion of water, a water-soluble azo dye having a specific structure and a dye. An ink set having a second ink containing ions is disclosed.

JP 2013-10826 A

  2. Description of the Related Art In recent years, the textile printing industry has been demanding a technique for coloring a fabric with a high concentration of black. Dark black is in demand, because it has the effect of producing a sense of quality and the effect of tightening and showing other colors to improve image clarity.

  According to the study of the present inventors, when the cloth was colored using the ink set of Patent Document 1 and the reflection density of black was examined, it was found that a sufficient reflection density could not be obtained.

  An object of the present invention is to provide an ink set capable of providing a colored cloth having excellent reflection density and image clarity, an ink jet printing method using the ink set, an ink cartridge having the ink set, and an ink jet printer. It is in.

  The present inventors have conducted intensive studies and found that the above-mentioned problems can be solved by the following means.

<1>
An ink set including an ink-jet ink (P) containing an aqueous dispersion of an oil-soluble dye represented by the following general formula (MA) and an ink-jet ink (Q) containing an aqueous dispersion of a pigment.

In Formula (MA), R ^{1 to} R ²⁰ each independently represent a hydrogen atom or a substituent.
<2>
The ink set according to <1>, wherein the inkjet ink (P) includes a self-dispersion pigment.
<3>
The oil-soluble dye is C.I. I. The ink set according to <1> or <2>, which is Solvent Black 3.
<4>
The pigment in the inkjet ink (Q) is
Carbon black,
Aniline black,
C. I. Pigment Yellow 3, 12, 53, 55, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 155, 180, 185,
C. I. Pigment Red 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219,
C. I. Pigment Violet 19, 23,
C. I. Pigment Orange 36, 43, 64,
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 56, 60, 63,
C. I. Pigment Green 36
The ink set according to any one of <1> to <3>, which is at least one member selected from the group consisting of:
<5>
The ink set according to any one of <1> to <4>, which is used for inkjet printing.
<6>
An ink-jet printing method including a step of directly printing on a fabric by an ink-jet method using the ink set according to any one of <1> to <5>.
<7>
A pretreatment step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated fabric, and an ink jet method using the ink set according to any one of <1> to <5>. An ink-jet printing method comprising a step of printing on the pretreated cloth.
<8>
The inkjet printing method according to <6> or <7>, further including a heat treatment step.
<9>
An ink cartridge comprising the ink set according to any one of <1> to <5>.
<10>
An inkjet printer comprising the ink set according to any one of <1> to <5>.

The reason why a colored cloth excellent in reflection density and image clarity can be obtained by using the ink set of the present invention is not clear, but is presumed as follows.
The ink set of the present invention includes an inkjet ink containing an aqueous dispersion of an oil-soluble dye represented by the general formula (MA). The oil-soluble dye represented by the general formula (MA) has a high solubility in a solvent, and thus can be dispersed in water at a high concentration, and has a high black color development density. However, if only the oil-soluble dye represented by the general formula (MA) is used, since the ink film obtained after heat fixing is smooth, light is reflected, and the color density of the used oil-soluble dye ( Reflection density). In the present invention, it is presumed that the pigment is present as particles on the print medium by further using an inkjet ink containing an aqueous dispersion of the pigment, and as a result, the oil represented by the general formula (MA) In the boundary area between the area printed with the soluble dye and the area printed with the pigment, the ink film after heat fixing becomes uneven, suppressing the reflection, sufficiently extracting the black reflection density of the oil-soluble dye, I guess it will be clearer.

  According to the present invention, there are provided an ink set capable of providing a colored cloth excellent in reflection density and image clarity, an ink jet printing method using the ink set, an ink cartridge having the ink set, and an ink jet printer. be able to.

It is an image pattern for evaluating image sharpness.

Hereinafter, the present invention will be described in detail.
In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.

In the present specification, the “substituent group A” refers to a substituent described in [0117] of WO 2017/131107.
In this specification, the substituent group A1 includes the following substituents.

(Substituent group A1)
Halogen atom, alkyl group (preferably having 1 to 30 carbon atoms), cycloalkyl group (preferably having 3 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), heterocyclic group (preferably having 3 to 30 carbon atoms) 30), an acyl group (preferably having 2 to 30 carbon atoms), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an alkoxy group (preferably having 1 to 30 carbon atoms), and an aryloxy group (preferably having 2 to 30 carbon atoms) 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, Amino group (preferably having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably having 1 to 30 carbon atoms), arylsulfonylamino group (preferably having 6 to 30 carbon atoms), and substitution obtained by combining two or more of these. Base.

  In the present invention, the ionic group such as a sulfo group or a carboxyl group may be in a state containing a cation or an anion (also referred to as a “salt state”). For example, the carboxyl group, the phosphate group, and the sulfo group may be in a state containing a cation. Examples of the cation that forms a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion). , Potassium ions) and organic cations (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).

[Ink jet ink containing water dispersion of oil-soluble dye represented by formula (MA) and self-dispersion pigment]
The inkjet ink containing the aqueous dispersion of the oil-soluble dye represented by the general formula (MA) is also referred to as “ink-jet ink (P)”. Hereinafter, the inkjet ink (P) will be described.

<Water dispersion of oil-soluble dye represented by general formula (MA)>
The inkjet ink (P) includes an aqueous dispersion of an oil-soluble dye represented by the following general formula (MA) (hereinafter, also simply referred to as an oil-soluble dye).

In Formula (MA), R ^{1 to} R ²⁰ 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).

In Formula (MA), R ¹ and R ² preferably independently represent a hydrogen atom, an alkyl group, or a hydroxyalkyl group.
Examples of the alkyl group represented by R ¹ and R ² include an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group. More preferably, it is represented.
Examples of the alkyl group in the hydroxyalkyl group represented by R ¹ and R ² include the same groups as the alkyl group represented by R ¹ and R ² , and the preferred range is also the same.
More preferably, R ¹ and R ² represent a hydrogen atom.

In Formula (MA), R ^{3 to} R ¹⁸ each preferably independently represent a hydrogen atom, an alkyl group, or a hydroxyalkyl group.
Examples of the alkyl group and hydroxyalkyl group represented by R ^{3 to} R ¹⁸ include the same groups as the alkyl group and hydroxyalkyl group represented by R ¹ and R ² , and the preferred range is also the same.
R ^{3 to} R ¹⁸ more preferably represent a hydrogen atom.

In Formula (MA), R ¹⁹ and R ²⁰ preferably each independently represent an alkyl group or a hydroxyalkyl group.
Examples of the alkyl group and hydroxyalkyl group represented by R ¹⁹ and R ²⁰ include the same groups as the alkyl group and hydroxyalkyl group represented by R ¹ and R ² , and the preferred range is also the same.
R ¹⁹ and R ²⁰ more preferably represent an alkyl group, more preferably a methyl group.

  Examples of the oil-soluble dye include C.I. I. Solvent Black 3 is most preferable.

  In the aqueous dispersion of the oil-soluble dye represented by Formula (MA), the oil-soluble dye may be used alone or in a combination of two or more.

  The inkjet ink (P) contains an aqueous dispersion of the oil-soluble dye represented by the general formula (MA), that is, contains water. The water used for the inkjet ink (P) is not particularly limited, and pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. It is more preferable to use ultrapure water.

The ink-jet ink (P) contains at least an aqueous dispersion of an oil-soluble dye represented by the general formula (MA), that is, the ink-jet ink (P) is a liquid containing water represented by the general formula (MA) It is a dispersion in which the oil-soluble dye represented by (MA) is dispersed.
The content of the aqueous dispersion of the oil-soluble dye represented by the general formula (MA) in the inkjet ink (P) is preferably 2 to 15% by mass, and more preferably 3 to 12% by mass. More preferably, it is 4 to 10% by mass. When the content is 2% by mass or more, color development can be performed at a high concentration, and when the content is 15% by mass or less, stable ejection can be performed, which is preferable.
The content of water in the inkjet ink (P) is preferably from 40 to 80% by mass, more preferably from 45 to 75% by mass, and still more preferably from 50 to 75% by mass. When the water content is within the above range, the stability of the ink is excellent (the sedimentation or the like is unlikely to occur), and the ejection stability as an inkjet ink is also excellent.

  The aqueous dispersion of the oil-soluble dye represented by the general formula (MA) may be, in addition to the oil-soluble dye and water, a dispersant for dispersing the oil-soluble dye, an aqueous organic solvent described below, Agents, lubricants, curing agents, initiators and the like.

In the aqueous dispersion of the oil-soluble dye represented by Formula (MA), the oil-soluble dye is preferably dispersed in water as colored resin particles containing the oil-soluble dye and a polymer.
Hereinafter, the colored resin particles containing the oil-soluble dye and the polymer will be described.

<Colored resin particles>
The average particle size of the colored resin particles containing the oil-soluble dye and the polymer is preferably 200 nm or less, more preferably 20 to 200 nm, and further preferably 40 to 150 nm. When the average particle diameter of the colored resin particles is 200 nm or less, it becomes easy to print on the fabric by the ink jet method.
As the average particle diameter of the colored resin particles, a value of a volume average particle diameter (MV) measured using a particle size distribution analyzer (Nanotrack UPA EX150, manufactured by Nikkiso Co., Ltd.) was used.

In the inkjet ink (P), it is preferable that the colored resin particles are present in a state of being dispersed in water.
When dispersed, the colored resin particles are easily mixed with water (easy to wet) as a property of the colored resin particles themselves or by using a dispersant in combination, and are regenerated by electrostatic repulsion (repulsive force) or steric repulsion. It has the function of preventing aggregation and suppressing sedimentation.
As a method for dispersing the colored resin particles, a known method can be used.

(polymer)
The colored resin particles used in the present invention preferably contain at least one polymer selected from the group consisting of (meth) acrylic polymers, polyurethanes and polyureas.

-Polyurethane Polyurethane is a polymer having a urethane bond, and can typically be synthesized by reacting a compound having two or more isocyanate groups with a compound having two or more hydroxyl groups.
Polyurethane may be synthesized by a known method, or a commercially available product may be used.

The polyurethane may have a crosslinked structure.
The crosslinked structure represents a structure obtained by using a compound having three or more hydroxyl groups or isocyanate groups in the molecule as at least one monomer.
Examples of the compound having three or more hydroxyl groups or isocyanate groups in the molecule include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, hexamethylene diisocyanate, biuret of toluene diisocyanate, isocyanurate, adduct and the like. Is mentioned.

The polyurethane may further have a urea bond. A resin having a urethane bond and a urea bond is also called “polyurethane / polyurea”.
As one kind of a preferable form of the polyurethane in the present invention, there is a polyurethane / polyurea in which a first partial structure containing a urethane bond and a second partial structure containing a urethane bond are bonded by a urea bond.

Further, the weight average molecular weight (Mw) of the polyurethane is preferably at least 1,000, more preferably at least 5,000, even more preferably at least 10,000. When the molecular weight is 10,000 or more, it is preferable from the viewpoint of securing fixability after heating and securing color fastness. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyurethane can be measured by gel permeation chromatography (GPC).
In the present specification, GPC was measured using HLC-8220GPC (manufactured by Tosoh Corporation), columns were measured using TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation) unless otherwise specified. The average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated in terms of polystyrene.

-Polyurea Polyurea is a polymer having a urea bond, and can be typically synthesized by reacting a compound having two or more isocyanate groups with a compound having two or more amino groups.
Polyurea may be synthesized by a known method, or a commercially available product may be used.

Polyurea may have a crosslinked structure.
The crosslinked structure represents a structure obtained by using a compound having three or more hydroxyl groups or isocyanate groups in the molecule as at least one monomer.
Examples of the compound having three or more hydroxyl groups or isocyanate groups in the molecule include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, hexamethylene diisocyanate, biuret of toluene diisocyanate, isocyanurate, adduct and the like. Is mentioned.

  The polyurea may further have a urethane bond. As described above, a resin having a urethane bond and a urea bond is also referred to as “polyurethane / polyurea”.

  Further, the weight average molecular weight (Mw) of the polyurea is preferably at least 1,000, more preferably at least 5,000, further preferably at least 10,000, particularly preferably at least 30,000. When the molecular weight is 30,000 or more, it is preferable from the viewpoint of securing fixability after heating and fastness of dyeing. The number average molecular weight (Mn) and weight average molecular weight (Mw) of polyurea can be measured by gel permeation chromatography (GPC).

-(Meth) acrylic polymer In the present invention, "(meth) acrylic polymer" represents at least one of an acrylic polymer and a methacrylic polymer.
As the (meth) acrylic polymer in the present invention, a commercially available product or a synthetic product may be used, and the synthetic product can be synthesized by a known radical polymerization method using a known monomer.

  Further, the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably at least 1,000, more preferably at least 5,000, further preferably at least 10,000, and even more preferably at least 30,000. Is particularly preferred. When the molecular weight is 30,000 or more, it is preferable from the viewpoint of securing fixability after heating and fastness of dyeing. The number average molecular weight (Mn) and weight average molecular weight (Mw) of polyurea can be measured by gel permeation chromatography (GPC).

  The polymer contained in the colored resin particles used in the present invention is preferably at least one selected from the group consisting of polyurethane and polyurea, from the viewpoint of improving the color density, improving the fastness and the like.

The acid value of the polymer is preferably from 5 to 90 mgKOH / g.
When the acid value is 5 mgKOH / g or more, when the colored resin particles are used as a dispersion, the dispersibility of the dispersion can be maintained, and the stability of the ink is not reduced. On the other hand, when the acid value is 90 mgKOH / g or less, the association of the dye by the water-soluble organic solvent is easily released, the dispersibility can be maintained, and the color density and the continuous ejection property of the ink are not reduced.
The acid value of the polymer is preferably from 5 to 90 mgKOH / g, more preferably from 10 to 90 mgKOH / g, particularly preferably from 10 to 80 mgKOH / g.

In consideration of the accuracy of the measurement, the acid value of the polymer was measured for the polymer particles prepared without adding a dye in the preparation of the colored resin particles.
The acid value can be measured according to the indicator titration method of JIS (Japanese Industrial Standard) K1557. However, the measurement is performed after removing the neutralizing agent used to neutralize the acidic group. For example, when an organic amine is used as a neutralizing agent, a colored resin particle dispersion or a 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 to remove the organic amine. After volatilization, the obtained coating film is dissolved in N-methylpyrrolidone, and the acid value can be measured according to the indicator titration method of JIS K1557.
Note that 760 mmHg is 101325 Pa.

In the ink set of the present invention, in an ink-jet printing method using an ink set including the ink-jet ink (P), a cross-linking method described below is used in order to further increase the adhesion between the fabric and the polymer and improve the image fastness. Agents can be used. Therefore, the polymer preferably has a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, or the like as a group capable of reacting with the crosslinkable group of the crosslinking agent.
In addition, it is also preferable not to use a crosslinking agent in the inkjet ink (P). It is also preferable that the colored resin particles in the inkjet ink (P) do not contain a crosslinking agent. Furthermore, it is also preferred that the polymer has no groups that can react with the crosslinkable groups of the crosslinking agent.

  The polymer in the colored resin particles is preferably contained in an amount of 5 to 80% by mass, and more preferably 5 to 60% by mass, based on the total mass of the colored resin particles, for ensuring the dispersibility, the coloring property, and the color fastness. More preferably, the content is more preferably from 10 to 60% by mass.

  The content of the oil-soluble dye represented by the general formula (MA) in the colored resin particles is 10 to 90% by mass with respect to the total mass of the colored resin particles because the color developing property and the color fastness are secured. %, More preferably 15 to 80% by mass, still more preferably 20 to 75% by mass, and particularly preferably 25 to 70% by mass.

  In the aqueous dispersion of the oil-soluble dye and the colored resin particles in the inkjet ink (P), the oil-soluble dye is present in a form coated with a polymer, and the polymer and the oil-soluble dye are not covalently bonded. Is preferred. Since the polymer and the oil-soluble dye are not bound by a covalent bond, the mobility of the oil-soluble dye is enhanced, and a high color density can be exhibited.

  The content of the colored resin particles in the inkjet ink (P) is preferably from 0.5 to 30% by mass, more preferably from 1.0 to 25% by mass, from the viewpoint of ensuring ejection stability and color developing properties. 0-20 mass% is more preferable, and 3.0-20 mass% is especially preferable.

It is preferable that the aqueous dispersion of the oil-soluble dye represented by the general formula (MA) is produced as the aqueous dispersion of the above-described colored resin particles.
The method for producing the aqueous dispersion of the colored resin particles is not particularly limited. When the polymer is a polyurethane, for example, the following method may be used. In the presence or absence of an organic solvent containing no active hydrogen-containing group in the molecule (eg, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide, etc.), a polymer having two or more isocyanate groups in one molecule A polyurethane is synthesized by subjecting an isocyanate, a polyol having two or more hydroxyl groups in one molecule, a polyol having an acidic group or a salt thereof to a urethanization reaction by a one-shot method or a multi-stage method to synthesize a polyurethane, and if necessary, the polyurethane After neutralization with a wetting agent, an oil-soluble dye is added, water is dropped to a place where the reaction solution is vigorously stirred, and then a water dispersion of the colored resin particles is removed by removing the solvent as necessary. Is obtained.

  Further, as a method for producing an aqueous dispersion of colored resin particles, a polyisocyanate having two or more isocyanate groups in one molecule, a polyol having two or more hydroxyl groups in one molecule, an acidic group-containing polyol or a polyol thereof in advance It is also possible to synthesize a prepolymer under the condition of an excess of isocyanate with a salt, add an oil-soluble dye, disperse it in water, and then add a chain extender to form an aqueous dispersion of colored resin particles. .

(Polyisocyanate)
The polyisocyanate that can be used in the method for producing the aqueous dispersion of colored resin particles is not particularly limited as long as the polyisocyanate contains two or more isocyanate groups in one molecule. Examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, and 2,6-diisocyanate methyl isocyanate. Aromatic, aliphatic and alicyclic organic diisocyanates such as proate, isophorone diisocyanate (IPDI), methylcyclohexane-2,4- (or 2,6-) diisocyanate, and 4,4′-methylenebis (cyclohexyl isocyanate); Or a multimer containing a polyfunctional isocyanate group such as a burette or isocyanurate thereof, or a polymer of these isocyanates Alone or a mixture may be mentioned.
In particular, from the viewpoint of weather resistance, an aliphatic and / or alicyclic organic diisocyanate compound is preferable. Specifically, aliphatic and alicyclic organic diisocyanates such as HDI, IPDI, dodecane diisocyanate, cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate are preferable. Diisocyanates or mixtures of these isocyanates are more preferred.

(Polyol)
The polyol that can be used in the method for producing the aqueous dispersion of the colored resin particles is not particularly limited as long as the polyol contains two or more hydroxyl groups in one molecule. For example, a polymer polyol or a low molecular weight polyol is used. can do. Examples of polym-polyols include polyether polyols, polyester polyols, polycarbonate polyols and the like.
The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a random copolymer of ethylene oxide and propylene oxide, a random copolymer of ethylene oxide and butylene oxide, and a block copolymer. Further, a polyether polyester polyol having an ether bond and an ester bond can be used.
The polyester polyol is not particularly limited, for example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate polyol, polyethylene seba Kate polyol, polybutylene sebacate polyol, poly-ε-caprolactone polyol, poly (3-methyl-1,5-pentylene adipate) polyol and the like can be mentioned.
Examples of the polycarbonate polyol include a linear aliphatic polycarbonate polyol, a branched aliphatic polycarbonate polyol, a polycarbonate polyol having an alicyclic structure in a main chain, and a polycarbonate polyol having an aromatic ring in a main chain.
The low-molecular-weight polyol is not particularly limited, but a low-molecular-weight diol can be used. For example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl- 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 Aliphatic diols having 2 to 9 carbon atoms such as -hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol , 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis ( Hydroxyethyl) cyclohexane, 2,7-norbornanediol, tetrahydrofuranmethanol, diols having an alicyclic structure having 6 to 12 carbon atoms such as 2,5-bis (hydroxymethyl) -1,4-dioxane, and the like. Can be. Further, as the low molecular weight polyol, a low molecular weight polyhydric alcohol such as trimethylolpropane, pentaerythritol, and sorbitol may be used.

  The polyol is a compound containing two or more hydroxyl groups, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol , 1,2-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol Linear aliphatic glycols such as polyethylene glycol, polypropylene glycol, 1,8-octanediol, 1,2-octanediol and 1,9-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, 2 Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, Aliphatic branched glycols such as 2-methyl-1,8-octanediol; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; glycerin, trimethylolethane, trimethylolpropane, tributy And polyfunctional glycols such as roll propane, pentaerythritol, and sorbitol; and these can be used alone or in combination of two or more, and can also be used as a copolymer of two or more.

(Acid-containing polyol or salt thereof)
The acidic group-containing polyol that can be used in the method for producing the aqueous dispersion of colored resin particles is a compound having two or more hydroxyl groups and one or more acidic groups in one molecule. It is used for introducing a carboxylate group or a sulfonate group for the purpose of self-emulsifying a colored resin in water and imparting dispersion stability of an aqueous dispersion of colored resin particles. The carboxyl group-containing polyol is not particularly limited. For example, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctane Acids and the like. Examples of the sulfone group-containing polyol include sulfonic acid diol {3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid} and sulfamic acid diol {N, N-bis (2-hydroxylalkyl) sulfamic acid. And an alkylene oxide adduct thereof. The salt of the polyol containing a carboxyl group and / or a sulfone group is not particularly limited, and examples thereof include ammonium salts, amine salts [primary amines having 1 to 12 carbon atoms (primary monoamines such as methylamine, ethylamine, propyl Amines and octylamine) salts, secondary monoamines (dimethylamine, diethylamine and dibutylamine) salts, tertiary monoamines (trimethylamine, triethylamine triethanolamine, N-methyldiethanolamine and aliphatic tertiary such as N, N-dimethylethanolamine) Monoamines; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; tertiary monoamines containing aromatic rings such as benzyldimethylamine, α-methylbenzyldimethylamine; and N-dimethylaniline ) Salts, alkali metal (sodium, potassium and lithium cations) salts, as well as combinations of two or more of these.

  When the polyol is not a salt but a carboxyl group and / or sulfone group-containing polyol, a neutralizing agent may be used to neutralize the carboxyl group and / or sulfone group to form a carboxylate group and / or sulfonate group. it can.

(Neutralizer)
The neutralizing agent is not particularly limited, and examples thereof include an alkaline compound capable of neutralizing the carboxyl group and / or the sulfone group. For example, ammonia, amine [a primary amine having 1 to 12 carbon atoms (primary monoamine such as methylamine, ethylamine, propylamine and octylamine), a secondary monoamine (dimethylamine, diethylamine and dibutylamine), and a tertiary monoamine ( Aliphatic tertiary monoamines such as trimethylamine, triethylamine, triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine; heterocyclic tertiary monoamines such as N-methylpiperidine and N-methylmorpholine; benzyldimethylamine; α-methylbenzyldimethylamine; and tertiary monoamines containing an aromatic ring such as N-dimethylaniline)], alkali metals (sodium, potassium and lithium cations), alkali metal hydroxides, and Combinations of two or more of the like.

(Chain extender)
Examples of the chain extender include, but are not limited to, water, short-chain diols such as ethylene glycol, 1,3-propanediol, and 1,4-butanediol, hydrazine, ethylenediamine, diethyltriamine, triethylenetetramine, and tetraethylene. Examples thereof include polyamines such as pentamine, pentaethylenehexamine, propylenediamine, hexamethylenediamine, and cyclohexylenediamine. These may be used alone or in combination of two or more.

  As a method for producing an aqueous dispersion of colored resin particles, when the polymer is polyurea, for example, an organic solvent containing no active hydrogen-containing group in the molecule (for example, acetone, methyl ethyl ketone, tetrahydrofuran, N, N-dimethylformamide) And the like in the presence or absence of a polyisocyanate having two or more isocyanate groups in one molecule, a polyamine having two or more amino groups in one molecule, an acidic group-containing polyol or a salt thereof. Polyurea is synthesized by a urethanation reaction according to a method or a multi-stage method, and if necessary, the above-mentioned polyurea is neutralized with a neutralizing agent, and then an oil-soluble dye is added. Is dropped, and the solvent is removed as necessary to obtain an aqueous dispersion of colored resin particles.

  Further, as a method for producing an aqueous dispersion of colored resin particles, a polyisocyanate having two or more isocyanate groups in one molecule, a polyamine having two or more amino groups in one molecule, an acid group-containing polyol or It is also possible to synthesize a prepolymer under the condition of an excess of isocyanate with a salt, add an oil-soluble dye, disperse it in water, and then add a chain extender to form an aqueous dispersion of colored resin particles. .

(Polyamine)
The polyamine that can be used in the method for producing the aqueous dispersion of the colored resin particles is not particularly limited as long as it is a polyamine containing two or more amino groups in one molecule, and for example, a polymer polyamine or a low molecular weight polyamine is used. can do.
The polymer polyamine is not particularly restricted but includes, for example, polyethyleneimine, polyethyleneoxy polymer terminal diamine, polyoxypropylene polymer terminal diamine, polyoxyethylene / oxypropylene copolymer terminal diamine, and the like.
The low molecular weight polyamine is not particularly limited, and examples thereof include ethylenediamine, propylenediamine, putrescine, hexamethylenediamine, spermidine, spermine, phenyldiamine, naphthalenediamine, xylenediamine, and isophoronediamine.

  As for the polyisocyanate, the acidic group-containing polyol or a salt thereof, the neutralizing agent, and the chain extender, the above-described polyisocyanate, the acidic group-containing polyol or a salt thereof, the neutralizing agent, and the chain extender can be used.

  When the polymer is a (meth) acrylic polymer, the aqueous dispersion of the colored resin particles can be synthesized by a known radical polymerization method using a known monomer. For example, it can be synthesized with reference to synthesis and reaction of a polymer (Kyoritsu Shuppan Co., Ltd.).

<Self-dispersible pigment>
The inkjet ink (P) preferably contains a self-dispersing pigment. By using a self-dispersing pigment in combination with the oil-soluble dye represented by the general formula (MA), a color density (reflection density) higher than that obtained with only the oil-soluble dye represented by the general formula (MA) ) Can be improved. By using a self-dispersing pigment in combination, the ink film after thermal fixing is roughened and the reflection is suppressed, whereby the reflection density of the oil-soluble dye can be further extracted.
In addition, the self-dispersion type pigment has a hydrophilic pigment surface and can prevent the oil-soluble dye from associating on the pigment surface when used together.

The self-dispersion pigment is a pigment that can be dispersed in water without using a dispersant. Self-dispersible pigments include, for example, a carbonyl group, a hydroxyl group, a carboxyl group, a sulfo group, a hydrophilic group such as a phosphoric acid group, and at least one of their salts, which are directly or via other groups, on the surface of the pigment. Those introduced by bonding may be mentioned.
The self-dispersing pigment is preferably a self-dispersing carbon black.
Examples of the self-dispersible pigments that can be used include self-dispersible carbon blacks CAB-O-JET 200, 300 (all manufactured by Cabot Corporation), BONJET CW-1 (500 μmol / g as a carboxy group), and CW-2 ( Commercially available products such as 470 μmol / g as a carboxy group (above, manufactured by Orient Chemical Industry Co., Ltd.) and Aqua-Black 162 (about 800 μmol / g as a carboxyl group) of Tokai Carbon Co., Ltd.

  Further, the ratio of the content of the self-dispersible pigment to the content of the oil-soluble dye represented by the general formula (MA) (content of the self-dispersible pigment / expressed by the general formula (MA)) (Oil-soluble dye content) is preferably 1/9 to 5/5, more preferably 2/8 to 3/7, by mass ratio.

<Aqueous organic solvent>
The inkjet ink (P) may further contain an aqueous organic solvent.
As the aqueous organic solvent, those having a water solubility of 10 g / 100 g-H ₂ O or more at 25 ° C. are preferable, those having a water solubility of 20 g / 100 g-H ₂ O or more are more preferable, and those that are miscible with water at an arbitrary ratio Is particularly preferred. Examples of the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents.

  The content of the aqueous organic solvent in the inkjet ink (P) is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. This range is preferable because the stability of the aqueous dispersion of the oil-soluble dye represented by Formula (MA) and the ejection stability as an inkjet ink can be imparted.

<Crosslinking agent>
The inkjet ink (P) may further contain a crosslinking agent.
As described above, in the ink jet printing method of the present invention, it is preferable to use a cross-linking agent in order to further increase the adhesion between the fabric and the polymer and improve the image fastness. It is preferable that the polymer and the component constituting the fabric be bonded by the crosslinking agent.
The crosslinking agent is preferably a compound having at least two crosslinking groups.
As the crosslinkable group of the crosslinking agent, a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group and the like are preferable.
Examples of the crosslinking agent include a blocked isocyanate compound, an oxazoline compound, and a carbodiimide compound. Among them, HDI (hexamethylene diisocyanate), H6XDI (hydrogenated xylylene diisocyanate), IPDI (isophorone diisocyanate), or H12MDI ( A blocked isocyanate compound obtained by blocking a TMP (trimethylolpropane) adduct of dicyclohexylmethane diisocyanate) or an isocyanurate with a blocking agent is preferable, and the blocking agent may be DEM (diethyl malonate), DIPA (diisopropyl) based on its dissociation temperature. Amine), TRIA (1,2,4-triazole), DMP (3,5-dimethylpyrazole), and MEKO (butanone oxime). That. In addition, these blocked isocyanate compounds can also be used as oligomers in which a part of the isocyanate group is reacted with polyol, polycarbonate, polyester, polyether, or the like.
The crosslinking agent is preferably added to the ink as a water-soluble or self-emulsifying agent by imparting a hydrophilic group. In this state, the viscosity of the compounded ink can be reduced, and excellent redispersibility can be obtained.

  The content of the cross-linking agent in the inkjet ink (P) is preferably 0.1 to 10% by mass because it is necessary to incorporate a cross-linkable functional group sufficient to cause the polymer and the fabric to react. , More preferably from 0.5 to 8% by mass, even more preferably from 1 to 5% by mass.

<Other ingredients>
The inkjet ink (P) may contain components other than those described above.
Other components include, for example, colorants other than the above dyes and self-dispersing pigments, organic solvents, surfactants, pH adjusters, fluorescent brighteners, surface tension adjusters, defoamers, anti-drying agents, lubrication Agents, thickeners, ultraviolet absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, resistivity adjusters, rust inhibitors, inorganic pigments, reduction inhibitors, preservatives, fungicides, and chelates Agents and the like. As these components, those described in WO 2017/131107 can be preferably used.

  The method for preparing the inkjet ink (P) is not particularly limited. For example, an aqueous dispersion of an oil-soluble dye represented by the general formula (MA), a self-dispersed pigment, and, if necessary, water and an aqueous organic solvent. Alternatively, it can be prepared by mixing with other components.

[Inkjet ink containing aqueous dispersion of pigment]
The inkjet ink containing the aqueous dispersion of the pigment is also referred to as “ink-jet ink (Q)”. The inkjet ink (Q) will be described.

(Aqueous dispersion of pigment)
The inkjet ink (Q) contains an aqueous dispersion of a pigment.
As a pigment water dispersion (also referred to as a “pigment water dispersion”), a pigment dispersion described in JP-A-2012-7148 can be used.

  The particle size of the pigment aqueous dispersion is preferably from 50 nm to 500 nm, more preferably from 60 nm to 400 nm, and still more preferably from 70 nm to 300 nm.

The pigment of the pigment aqueous dispersion in the present invention is
Carbon black,
Aniline black,
C. I. Pigment Yellow 3, 12, 53, 55, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 155, 180, 185,
C. I. Pigment Red 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219,
C. I. Pigment Violet 19, 23,
C. I. Pigment Orange 36, 43, 64,
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 56, 60, 63,
C. I. Pigment Green 36
It is preferably at least one member selected from the group consisting of:

The addition amount of the pigment in the pigment aqueous dispersion in the invention is preferably 0.5 to 30% by mass, and more preferably 1.0 to 15% by mass. When the addition amount of the pigment is 0.5% by mass or more, the print density becomes high, and when the amount is 30% by mass or less, it is difficult for the viscosity of the ink to increase or structural viscosity to occur in the viscosity characteristics, and the It is preferable because of excellent ejection stability.
As the pigment, a self-dispersion pigment can be used. Examples of the self-dispersible pigment that can be used include the self-dispersed pigment that can be used in the above-described inkjet ink (P).
The pigments can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

(Other components)
The inkjet ink (Q) may contain polymer fine particles. As the polymer fine particles, polymer fine particles described in JP-A-2012-7148 can be used. As the polymer fine particles, a crosslinkable polyurethane and / or a crosslinkable polyurethane-polyurea are preferably used.
The inkjet ink (Q) may contain 1,2-alkylene glycol, glycol ether, or a water-soluble organic solvent. Preferred embodiments of these are those described in JP-A-2012-7148.
The ink-jet ink (Q) may contain other components other than those described above. Other components include, for example, colorants other than the above pigments, crosslinking agents, organic solvents, surfactants, penetration inhibitors, pH adjusters, fluorescent brighteners, surface tension adjusters, defoamers, drying inhibitors , Lubricants, thickeners, ultraviolet absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, resistivity adjusters, rust inhibitors, inorganic pigments, reduction inhibitors, preservatives, fungicides, And a chelating agent.
The crosslinking agent that may be included in the inkjet ink (Q) is the same as the crosslinking agent that may be included in the inkjet ink (P) described above.

The inkjet ink (Q) contains at least an aqueous dispersion of a pigment, that is, the inkjet ink (Q) is a dispersion liquid in which a pigment is dispersed in a liquid containing water.
The content of the pigment in the inkjet ink (Q) is preferably from 0.5 to 30% by mass, and more preferably from 1 to 15% by mass.
The content of water in the inkjet ink (Q) is preferably from 40 to 90% by mass, and more preferably from 50 to 80% by mass.
The method for preparing the ink-jet ink (Q) is not particularly limited. For example, the ink-jet ink (Q) can be prepared by mixing an aqueous dispersion of a pigment with water or other components as needed.

The surface tension of the inkjet ink (P) and the inkjet ink (Q) is preferably adjusted to 20 mN / m to 70 mN / m, and more preferably adjusted to 25 mN / m to 60 mN / m. Further, the viscosity of the inkjet ink (P) and the inkjet ink (Q) is preferably adjusted to 40 mPa · s or less, more preferably to 30 mPa · s or less, and particularly preferably to 20 mPa · s or less. preferable. The viscosity is measured at 25 ° C. using an E-type rotational viscometer.
The surface tension and the viscosity are determined by various additives such as a viscosity modifier, a surface tension regulator, a specific resistance regulator, a film regulator, an ultraviolet absorber, an antioxidant, a discoloration inhibitor, a fungicide, and a rust inhibitor. It can be adjusted by adding a dispersant, a surfactant and the like.

[Ink set]
The ink set of the present invention includes an inkjet ink (P) and an inkjet ink (Q).
The ink set of the present invention may include two or more types of inkjet inks (P), and may include two or more types of inkjet inks (Q). That is, the ink set of the present invention only needs to include at least one type of inkjet ink (P) and at least one type of inkjet ink (Q).
In addition, the ink set of the present invention preferably contains at least a black ink, and preferably contains at least another colored ink in addition to the black ink. For example, the ink set may be selected from a magenta ink, a yellow ink, and a cyan ink. It is preferable to include at least one type of colored ink.
More specific embodiments include those shown in the following (1), but the present invention is not limited thereto.
(1) The inkjet ink (P) is a black ink, and the inkjet ink (Q) is at least one of a magenta ink, a yellow ink, and a cyan ink.

  The ink set of the present invention is preferably used for inkjet printing.

[Inkjet printing method]
The ink-jet printing method of the present invention is an ink-jet printing method including a step of printing on a fabric by an ink-jet method using the ink set of the present invention. The following two embodiments are preferable embodiments.
First aspect: An ink-jet printing method including a step of directly printing on a fabric by an ink-jet method using the ink set of the present invention.
Second aspect: a pretreatment step of applying a water-based pretreatment liquid containing a flocculant to the fabric to obtain a pretreated fabric, and directly using the ink set of the present invention to fabric pretreated by an inkjet method. An inkjet printing method having a printing step.
In the present invention, "direct printing" on the fabric by the ink jet method does not require a transfer step, and the ink jet ink is directly printed on the fabric, and a step of applying a printing paste is unnecessary. It refers to both the fact that the inkjet ink is printed directly on the fabric.
INDUSTRIAL APPLICABILITY The ink jet printing method of the present invention does not generate waste materials such as wastewater and transfer paper, and has an effect of being excellent in quality (feel) of a colored cloth, image clarity and fastness to wet friction with simple workability.

(Pretreatment step)
The pretreatment step in the second aspect is a step of applying an aqueous pretreatment liquid containing a flocculant to the fabric to obtain a pretreated 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 inkjet method, a spray method, and a screen printing method.
The coagulant contained in the aqueous pretreatment liquid is not particularly limited as long as it has an action of coagulating the above-mentioned colored resin particles containing the oil-soluble dye represented by the general formula (MA). , A polyvalent metal salt, and a cationic compound.
In particular, when the flocculant is a cationic compound or a polyvalent metal salt, and the polymer in the colored resin particles has an anionic group (preferably an acid group), when the image is printed by the above-mentioned inkjet printing method, a high density A colored cloth can be obtained. This is because the pre-treated cationic compound or polyvalent metal salt aggregates at the moment of contact with the ink containing the colored resin particles having an anionic group and stays on the fabric surface, resulting in a surface It is considered that the amount of the colored resin particles present in the dye increases and the concentration of the dye can be increased. More preferably, the flocculant is a cationic compound.

≪Polyvalent metal salt≫
A 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 And the like.

≪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, Hydroxy-4- (trimethylammonio) butyrate hydrochloride, glycidyltrimethylammonium chloride, L-carnitine hydrochloride and the like can be mentioned.
Examples of the high molecular weight cationic compound include, for example, polyallylamine or a derivative thereof, an amine-epihalohydrin copolymer, and other quaternary ammonium salt-type cationic polymers, which are soluble in water and positively formed in water. Chargeable cationic polymers can be mentioned. In some cases, a water-dispersible cationic polymer may be used.

The coagulants may be used alone or in combination of two or more.
The aqueous pretreatment liquid may contain, for example, a surfactant and a resin in addition to water and an aqueous organic solvent.

  The inkjet printing method of the present invention further includes a heating step, whereby the colored resin particles are fused to the fibers of the fabric, thereby further integrating with the fibers, without impairing the texture, and improving the friction resistance and the like. There is an advantage that it can be further provided.

(Heat treatment process)
The inkjet 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 colored resin particles can be melted (or softened), and the adhesion to the fiber can be increased (that is, the heat treatment allows the dyeing to be performed. Can be). After drying, the colored cloth is preferably subjected to heat treatment for the purpose of melt-dyeing, usually at 100 to 250 ° C, more preferably at 100 ° C to 200 ° C, and particularly preferably at 120 ° C to 200 ° C. The heat treatment is preferably performed for 30 seconds to 3 minutes. When a reactive group is introduced into the polymer in the colored resin particles and a crosslinking agent is used in combination with the additive, the reactive group introduced into the polymer in the colored resin particle or the additive is used in this heat treatment step. It is preferable from the viewpoint of friction resistance that a cross-linking reaction be performed using the cross-linking agent.

(Post-processing)
The fabric (colored cloth) colored by the inkjet printing method of the present invention has excellent texture flexibility and fastness (friction resistance). However, if necessary, the entire surface of the colored cloth may be padded with a post-treatment agent. Thus, it is possible to obtain a colored cloth having further improved texture flexibility and fastness (especially rub resistance).

(Cloth)
Fabrics to which the inkjet printing method of the present invention can be applied include the following. Fabrics (fiber types) 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 nonwoven fabrics thereof. Is mentioned.
As the cloth, a pretreated cloth can be used. The pretreatment liquid can be applied by a coating method, a padding method, an inkjet method, a spray method, a screen printing method, or the like. The pretreatment liquid contains an aggregating agent for aggregating the dye polymer, and is preferably an aqueous solution. Examples of the coagulant include an organic acid, a polyvalent metal salt, and a cationic compound.
Clothing 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 set of the present invention and an ink jet printer having the ink set of the present invention.

(Synthesis of polyurethane resin U-1)
In a closed reaction vessel equipped with a thermometer and a stirrer, 7.9 parts by mass of poly (caprolactone) diol (number average molecular weight 530), 5.0 parts by mass of 2,2-dimethylolbutanoic acid (DMBA), 12.3 parts by mass of methylene diisocyanate (HDI), 0.67 parts by mass of trimethylolpropane and 70.0 parts by mass of tetrahydrofuran were charged, and Neostan U-600 (trade name, manufactured by Nitto Kasei Kogyo Co., Ltd.) was used as a catalyst. 09 parts by mass. The mixture was stirred at a temperature of 65 ° C. for 4 hours. Tetrahydrofuran was added thereto to adjust the solid content to 30% by mass. Thus, a tetrahydrofuran solution of the polyurethane resin U-1 was prepared.

(Synthesis of polyurethane resin U-2)
In a closed reaction vessel equipped with a thermometer and a stirrer, 9.2 parts by mass of poly (caprolactone) diol (number average molecular weight 530), 5.7 parts by mass of 2,2-dimethylolbutanoic acid (DMBA), 14.3 parts by mass of methylene diisocyanate (HDI), 0.77 parts by mass of trimethylolpropane and 70.0 parts by mass of tetrahydrofuran were charged, and Neostan U-600 (trade name, manufactured by Nitto Kasei Kogyo Co., Ltd.) was used as a catalyst. 09 parts by mass. The mixture was stirred at a temperature of 65 ° C. for 4 hours. Tetrahydrofuran was added thereto to adjust the solid content to 30% by mass. Thus, a tetrahydrofuran solution of the polyurethane resin U-2 was prepared.

<Preparation of oil-soluble dye aqueous dispersion (1)>
C. I. Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) at a concentration of 30% by mass in tetrahydrofuran heated at 50 ° C. at 21.9 parts by mass, and a 30% by mass solution of polyurethane resin U-1 in tetrahydrofuran 4.0 parts by mass, 0.9 mol equivalent of triethylamine with respect to the carboxyl group in the polyurethane resin U-1, and 13.0 parts by mass of tetrahydrofuran were mixed. To this, 47.3 parts by mass of a 1% by mass aqueous solution of sodium dodecyl sulfate was mixed and emulsified using a homogenizer (ED-1 manufactured by Nippon Seiki Co., Ltd.) at 16,000 rpm for 12 minutes. After the obtained emulsion was filtered using a 1-micron filter, the mixture was stirred at 45 ° C. for 4 hours under aeration and stirring conditions, and the organic solvent was distilled off. 2.3 parts by mass of a 10% by mass aqueous solution of UCAT SA102 was added, and ultrapure water was further added so as to have a solid concentration of 20% by mass to obtain an oil-soluble dye aqueous dispersion (1). The oil-soluble dye aqueous dispersion (1) was an aqueous dispersion of colored resin particles containing an oil-soluble dye and a polymer, and the volume average particle diameter (MV) of the colored resin particles was 207 nm.

<Preparation of oil-soluble dye aqueous dispersion (2)>
C. I. 21.9 parts by mass of Solvent Black 3 (trade name: Oil Black 860, manufactured by Orient Chemical Industries) at a concentration of 30% by mass in tetrahydrofuran heated at 50 ° C., and a 30% by mass solution of polyurethane resin U-2 in 30% by mass of tetrahydrofuran 4.0 parts by mass, 0.9 mol equivalent of triethylamine with respect to the carboxyl group in the polyurethane resin U-2, and 13.0 parts by mass of tetrahydrofuran were mixed. To this, 47.3 parts by mass of a 1% by mass aqueous solution of sodium dodecyl sulfate was mixed and emulsified using a homogenizer (ED-1 manufactured by Nippon Seiki Co., Ltd.) at 16,000 rpm for 12 minutes. After the obtained emulsion was filtered using a 1-micron filter, the mixture was stirred at 45 ° C. for 4 hours under aeration and stirring conditions, and the organic solvent was distilled off. 2.3 parts by mass of a 10% by mass aqueous solution of UCAT SA102 was added, and ultrapure water was further added so as to have a solid concentration of 20% by mass to obtain an oil-soluble dye aqueous dispersion (2). The oil-soluble dye aqueous dispersion (2) was an aqueous dispersion of colored resin particles containing an oil-soluble dye and a polymer, and the volume average particle diameter (MV) of the colored resin particles was 207 nm.

<Preparation of inkjet ink (Pb1)>
The following components were mixed at room temperature (20 ° C.), stirred for 15 minutes, and then filtered through a membrane filter (average pore size: 0.8 μm) to prepare an inkjet ink (Pb1). The inkjet ink (Pb1) is a black ink.
2.55 g of oil-soluble dye aqueous dispersion (1)
CAB-O-JET200 1.21 g
1.29 g of ultrapure water
Surfynol 104GP50 0.16g
2.80 g of tetraethylene glycol

<Preparation of inkjet ink (Pb2)>
An ink-jet ink (Pb2) was prepared in the same manner as in the preparation of the ink-jet ink (Pb1) except that the water-soluble oil-dispersible dye dispersion (1) was replaced with the oil-soluble dye water dispersion (2).

<Preparation of inkjet ink (Pb3)>
An inkjet ink (Pb3) was prepared in the same manner except that Aqua Black 162 (manufactured by Tokai Carbon Co., Ltd.) was used instead of CAB-O-JET200.

<Preparation of inkjet ink (Pb4)>
The following components were mixed at room temperature (20 ° C.), stirred for 15 minutes, and then filtered through a membrane filter (average pore size: 0.8 μm) to prepare an inkjet ink (Pb4). The inkjet ink (Pb4) is a black ink.
3.17 g of oil-soluble dye aqueous dispersion (1)
CAB-O-JET200 0.16 g
Ultra pure water 1.08g
Surfynol 104GP50 0.14g
2.45 g of tetraethylene glycol

<Preparation of inkjet ink (Pb5)>
The following components were mixed at room temperature (20 ° C.), stirred for 15 minutes, and then filtered through a membrane filter (average pore size: 0.8 μm) to prepare an inkjet ink (Pb5). The inkjet ink (Pb5) is a black ink.
2.27 g of oil-soluble dye aqueous dispersion (1)
Ultra pure water 0.88g
Surfynol 104GP50 0.10g
1.75 g of tetraethylene glycol

[Preparation of inkjet ink (Pb6)]
C.I. in aqueous dispersion of oil-soluble dye (Pb1). I. Solvent Black 3 instead of Solvent Black 3. I. An ink-jet ink (Pb6) was prepared in the same manner as in the preparation of the ink-jet ink (Pb1) except that Solvent Black 5 was used. The inkjet ink (Pb6) is a black ink.

[Preparation of inkjet ink (Qm)]
<Preparation of aqueous pigment dispersion (1)>
3 g of a styrene-acrylic acid copolymer (Joncryl 678, manufactured by BASF, trade name), 1.3 g of dimethylaminoethanol, and 80.7 g of ion-exchanged water were stirred and mixed at 70 ° C. Then, C.I. I. Pigment Red 112 and 15% by volume of zirconia beads having a particle size of 0.5 mm were dispersed at 50% by volume using a sand grinder mill to obtain a pigment dispersion (1) having a pigment content of 15% by mass. .

<Preparation of aqueous binder>
50 g of 2-butanone was placed in a three-necked flask, and the internal temperature was heated to 75 ° C., and a mixture of 80 g of n-butyl methacrylate, 20 g of acrylic acid, 50 g of 2-butanone, and 0.5 g of azoisobutyronitrile was added thereto for 3 hours. The solution was dropped. After the dropwise addition, the mixture was heated under reflux for 5 hours, cooled to room temperature, and heated under reduced pressure to obtain a polymer residue. 350 mL of ion-exchanged water and 1.05 times mol of sodium hydroxide of acrylic acid added as a monomer were added and dissolved therein. The mixture was diluted with ion-exchanged water so that the total amount was 500 g, to obtain a 20% by mass aqueous solution of an aqueous binder.

<Preparation of inkjet ink (Qm)>
46.6 g of the pigment dispersion (1), 15 g of a 20% by weight aqueous solution of the aqueous binder, 2.9 g of PDX-7664A (trade name, manufactured by BASF), 10 g of triethylene glycol monobutyl ether, 5 g of 1,2-hexanediol , Diethylene glycol 11.2 g, and Olfin 465 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.) 0.6 g, and ion-exchanged water was added thereto to adjust the total amount to 100 g. The mixture was filtered through a 0.8 μm filter, and inkjet was performed. An ink (Qm) was obtained. The inkjet ink (Qm) is a magenta ink. The particle size of the aqueous dispersion of the pigment in the ink was 109 nm.

[Preparation of inkjet ink (Qc)]
C.I in the pigment dispersion (1). I. Pigment Red 112, and C.I. I. An inkjet ink (Qc) was prepared in the same manner as in the preparation of the inkjet ink (Qm) except that Pigment Blue 15: 4 was used. The inkjet ink (Qc) is a cyan ink. The particle size of the aqueous dispersion of the pigment in the ink was 130 nm.

[Preparation of inkjet ink (Qy)]
C.I in the pigment dispersion (1). I. Pigment Red 112, and C.I. I. An ink-jet ink (Qy) was prepared in the same manner as in the preparation of the ink-jet ink (Qm) except that Pigment Yellow 180 was used. The inkjet ink (Qy) is a yellow ink. The particle size of the aqueous dispersion of the pigment in the ink was 117 nm.

[Preparation of inkjet ink (Qb)]
C.I in the pigment dispersion (1). I. An inkjet ink (Qb) was prepared in the same manner as in the preparation of the inkjet ink (Qm) except that carbon black was used instead of Pigment Red 112. The inkjet ink (Qb) is a black ink. The particle size of the aqueous dispersion of the pigment in the ink was 99 nm.

<Preparation of inkjet ink (Pb7)>
The following components were mixed at room temperature (20 ° C.), stirred for 15 minutes, and then filtered through a membrane filter (average pore size: 0.8 μm) to prepare an inkjet ink (Pb7). The inkjet ink (Pb7) is a black ink.
3.17 g of oil-soluble dye aqueous dispersion (1)
0.45g carbon black
Ultra pure water 0.78g
Surfynol 104GP50 0.14g
2.45 g of tetraethylene glycol

[Preparation of inkjet ink (Rm)]
(Preparation of dye aqueous dispersion 1)
The dye C.I. I. Disperse Red 60 (10 parts by mass), Demol NL (manufactured by Kao Corporation) (6 parts by mass), water (84 parts by mass), and zirconia beads having a diameter of 0.1 mm are mixed, and a planetary particle mill (Fritsch Inc.) Using a Pulverl set 7 manufactured by Co., Ltd.) at 400 rpm (revolution per minute) for 10 hours to obtain a dispersion. The zirconia beads were removed from the obtained dispersion using a filter cloth to obtain a water-insoluble dye aqueous dispersion 1. The average particle diameter of the dye aqueous dispersion 1 was 90 nm.
Demol NL is a dispersant.

Dye water dispersion 1 (30 parts by mass) obtained above, glycerin (10 parts by mass), propylene glycol (20 parts by mass), BYK-348 (manufactured by BYK Japan KK) (0.4 parts by mass), polyester Resin Vironal MD-1480 (also referred to as "MD1480") (manufactured by Toyobo Co., Ltd., solid content 30% by mass (water other than solid content), volume average particle diameter (Mv): 110 nm) (30 parts by mass), and water (9.6 parts by mass), and the mixture was filtered through a membrane filter (pore size: 0.8 μm) to prepare an inkjet ink (Rm).
Glycerin and propylene glycol are aqueous organic solvents, and BYK-348 is a surfactant.
The inkjet ink (Rm) is a magenta ink.

[Preparation of inkjet ink (Rc)]
As a dye, C.I. I. Instead of Disperse Red 60, C.I. I. An inkjet ink (Rc) was prepared in the same manner as the inkjet ink (Rm) except that Disperse Blue 359 was used. The average particle size was 115 nm. The inkjet ink (Rc) is a cyan ink.

[Preparation of inkjet ink (Ry)]
As a dye, C.I. I. Instead of Disperse Blue 359, C.I. I. An ink-jet ink (Ry) was prepared in the same manner as the ink-jet ink (Rc) except that Disperse Yellow 54 was used. The average particle size was 103 nm. The inkjet ink (Ry) is a yellow ink.

[Preparation of ink set for inkjet printing]
Ink jet printing ink sets 1 to 9 were prepared using combinations of the ink jet inks shown in Table 1 below.

(Preparation of aqueous pretreatment liquid A (1) containing coagulant)
Aqueous pretreatment liquid A (1) was prepared by mixing and stirring the following components. Katiomaster PD-7 contains a cationic compound as a flocculant.
Katiomaster PD-7 (manufactured by Yokkaichi Gosei, solid content 50% by mass)
50g
BYK348 (made by Big Chemie Japan) 5g
Glycerin 100g
845 g of water

(Pretreatment step)
The aqueous pretreatment liquid A (1) prepared above was applied to a polyester fabric (polyester tropical (manufactured by Teijin Limited), product number A02-01019, manufactured by Shisen Co., Ltd.) by a padding method, and a drawing ratio of 70% was applied. And dried for 24 hours. The squeezing ratio (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid with respect to the cloth after squeezing the cloth containing the aqueous treatment liquid.

<Example 1>
(Inkjet printing process)
The ink set 1 for ink-jet printing is loaded into an ink cartridge, and an image is printed on the pretreated polyester cloth using an ink-jet printer (Calario PX-045A, manufactured by Seiko Epson Corporation). Let dry for hours. After drying, using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press AF-54TEN type), a temperature of 200 ° C., a pressure of 0.20 N / cm ² , and a heat treatment for 60 seconds, A colored cloth was obtained.

<Examples 2 to 6>
Ink jet printing was performed in the same manner as in Example 1 except that the ink sets for ink jet printing 2 to 6 were used instead of the ink set 1 for ink jet printing, thereby obtaining a colored cloth.

<Comparative Examples 1 to 3>
Inkjet printing was carried out in the same manner as in Example 1 except that the ink sets for ink jet printing 7 to 9 were used instead of the ink set 1 for ink jet printing to obtain a colored cloth.

[Evaluation]
(Reflection density)
For the colored cloths obtained in each of the examples and comparative examples, using a spectrodensitometer (manufactured by X-rite, "X-rite938"), a density filter (ISO status A), a density white standard (absolute white standard) The CMYB density was measured under the conditions of no polarizing filter and a viewing angle of 2 °, and the reflection density of B (Black) was measured. The OD (Optical Density) value was evaluated based on the following criteria.
A: OD value 1.7 or more B: OD value 1.6 or more and less than 1.7 C: OD value less than 1.6

(Image sharpness)
The image pattern for evaluation shown in FIG. 1 was printed on a cotton fabric (with cotton broadsil, product code A02-01002) using the ink set for ink jet textile printing, and the sensory evaluation was visually conducted. went. Eight or more out of 10 persons, A, when the magenta, yellow, and cyan color portions look tight and the image is clear, B when 5 to 8 persons are clear, The case where less than 5 people answered clearly was C.
A method for creating an image pattern for evaluation is described below.
The prepared ink set for ink jet textile printing was loaded into an ink cartridge, and the image pattern shown in FIG. 1 was applied to the pretreated polyester fabric using an ink jet printer (Calario PX-045A, manufactured by Seiko Epson Corporation). And dried at 20 ° C. for 12 hours. After drying, using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press AF-54TEN), a heat treatment is performed at a temperature of 200 ° C., a pressure of 0.20 N / cm ² and a time of 60 seconds. Thus, a colored cloth having an image pattern was obtained.
In FIG. 1, B indicates a portion printed in black using black ink, M indicates a portion printed in magenta using magenta ink, and Y indicates a portion printed in yellow using yellow ink. C indicates a portion printed in cyan using cyan ink. The size of the black portion is 50 mm × 50 mm, and the size of the magenta, yellow, and cyan color portions is 5 mm × 5 mm. The distance between the magenta and yellow parts is 3 mm, and the distance between the yellow and cyan parts is 3 mm.

  As is evident from Table 2, when the ink set of the present invention was used, a colored cloth excellent in both reflection density and image clarity was obtained.

1 For black, an image pattern for evaluating the effect of tightening other colors B A portion printed in black C A portion printed in cyan Y A portion printed in yellow M A portion printed in magenta

Claims (10)

An ink set including an inkjet ink (P) containing an aqueous dispersion of an oil-soluble dye represented by the following general formula (MA) and an inkjet ink (Q) containing an aqueous dispersion of a pigment.

In Formula (MA), R ^{1 to} R ²⁰ each independently represent a hydrogen atom or a substituent.   The ink set according to claim 1, wherein the inkjet ink (P) includes a self-dispersing pigment.   The oil-soluble dye is C.I. I. The ink set according to claim 1, wherein the ink set is Solvent Black 3. The pigment in the inkjet ink (Q) is:
Carbon black,
Aniline black,
C. I. Pigment Yellow 3, 12, 53, 55, 74, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 155, 180, 185,
C. I. Pigment Red 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219,
C. I. Pigment Violet 19, 23,
C. I. Pigment Orange 36, 43, 64,
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 56, 60, 63,
C. I. Pigment Green 36
The ink set according to any one of claims 1 to 3, wherein the ink set is at least one selected from the group consisting of:   The ink set according to any one of claims 1 to 4, which is used for inkjet printing.   An ink-jet printing method comprising a step of directly printing on a fabric by an ink-jet method using the ink set according to any one of claims 1 to 5.   A pretreatment step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated fabric, and using the ink set according to any one of claims 1 to 5, wherein the ink-jet method is used. An ink jet printing method including a step of printing on a pretreated fabric.   The inkjet printing method according to claim 6, further comprising a heat treatment step.   An ink cartridge comprising the ink set according to claim 1.   An ink jet printer comprising the ink set according to claim 1.

Images