WO2018163966A1

WO2018163966A1 - Ink, ink jet textile printing method, ink cartridge, ink jet printer, and colored cloth

Info

Publication number: WO2018163966A1
Application number: PCT/JP2018/007846
Authority: WO
Inventors: 藤江　賀彦; 誠大元; 小林　博美; 未奈子原
Original assignee: 富士フイルム株式会社
Priority date: 2017-03-06
Filing date: 2018-03-01
Publication date: 2018-09-13

Abstract

The present invention provides an ink for ink jet textile printing including an aqueous dispersion of a polymer, which has a structure derived from a dye, and a pigment; an ink jet textile printing method using the ink for ink jet textile printing; an ink cartridge having the ink for ink jet textile printing; an ink jet printer; and a colored cloth including a polymer having a structure derived from a dye, and a pigment, hence, an ink for ink jet textile printing capable of providing a colored cloth excellent in image clarity and wet rubbing fastness, an ink jet textile printing method using the ink for ink jet textile printing, an ink cartridge having the ink for ink jet textile printing, an ink jet printer, and the colored cloth can be provided.

Description

Ink, inkjet printing method, ink cartridge, inkjet printer, and colored cloth

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

Ink-jet 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 it has environmental advantages such as less waste liquid. It can be said that this is an excellent printing method.

For example, Patent Document 1 describes an ink jet textile printing method using a pigment. In this method, a pigment and a surfactant as a dispersant are mixed in water and then finely dispersed with an attritor or a mill machine together with glass beads, zirconia beads, titania beads, or stainless steel balls, etc., are used as a colorant. It has been. Then, this colorant is diluted with a reducer containing an emulsion resin for fixing the pigment, a pigment ink is prepared, adhered to the fiber by an ink jet method, and the resin is fused by a heating roller to fix the pigment. .
Patent Documents 2 and 3 describe ink-jet inks containing a polymer linked with a dye.

Japanese Unexamined Patent Publication No. 2010-37700 Japan Special Table 2004-534106 Japan Special Table 2002-509957

However, the ink jet textile printing using the ink containing the pigment described in Patent Document 1 cannot be said to be excellent in image sharpness and wet friction fastness.
Further, Patent Documents 2 and 3 do not specifically disclose textile printing, and do not describe any of the above problems.

An object of the present invention is to provide an ink capable of providing a colored cloth excellent in image sharpness and fastness to wet friction, an ink jet printing method using the ink, an ink cartridge and an ink jet printer having the ink, and the colored cloth. Is to provide.

The problem of the present invention has been solved by the following means. Although the details of the reason why the above problems have been solved by the ink of the present invention have not been clarified, it is considered that a polymer having a structure derived from a dye corrects a color that cannot be colored only with a pigment.

<1>
An ink comprising an aqueous dispersion of a polymer having a structure derived from a dye, and a pigment.
<2>
The ink according to <1>, which is for inkjet textile printing.
<3>
The pigment 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 according to <1> or <2>, which is at least one selected from the group consisting of:
<4>
The structure derived from the dye is a structure derived from any dye selected from an azo compound, stilbene, triarylmethane, xanthene, indoaniline, indophenol, nigrosine, anthraquinone, quinophthalone, dicyanostyryl compound, and phthalocyanine. The ink according to any one of <1> to <3>.
<5>
The ink according to any one of <1> to <4>, wherein the polymer having a structure derived from the dye is polyurethane.
<6>
The ink according to any one of <1> to <5>, wherein the polymer having a structure derived from the dye is a polymer having a crosslinked structure.
<7>
The ink according to any one of <1> to <6>, wherein the polymer having a structure derived from the dye melts at 200 ° C.
<8>
The ink according to any one of <1> to <7>, wherein the ink further comprises an aqueous dispersion of a water-insoluble polymer having no structure derived from a dye.
<9>
<1> to <8> An inkjet printing method comprising a step of directly printing the ink according to any one of <8> on a fabric by an inkjet method.
<10>
An aqueous pretreatment liquid containing an aggregating agent is applied to a fabric to obtain a pretreated fabric, and the ink according to any one of <1> to <8> is used in an ink jet method. An inkjet printing method comprising a step of printing on a pretreated fabric.
<11>
Furthermore, the inkjet textile printing method as described in <9> or <10> including a heat processing process.
<12>
The inkjet printing method according to <11>, wherein the polymer having a structure derived from the dye is melted in the heat treatment step.
<13>
An ink cartridge having the ink according to any one of <1> to <8>.
<14>
<1> to <8> An inkjet printer having the ink according to any one of <8>.
<15>
A colored fabric comprising a fabric, a polymer having a structure derived from a dye, and a pigment.

According to the present invention, an ink that can provide a colored cloth excellent in image sharpness and fastness to wet friction, an ink jet printing method using the ink, an ink cartridge and an ink jet printer having the ink, and the colored cloth Can be provided.

It is a figure which shows UV (ultraviolet) absorption spectrum in chloroform / methanol = 1/1 solution about (M-1-1). It is an image pattern for evaluating the effect of tightening other colors for black.

Hereinafter, the present invention will be described in detail.
In the present 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, the “substituent selected from substituent group A” refers to substituents described in [0012] to [0051] of International Publication No. 2015/199135.
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, Alkylsulfonyl group (preferably having 1 to 30 carbon atoms), arylsulfonyl group (preferably having 6 to 30 carbon atoms), amino group, 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.

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 state include an ammonium ion, an alkali metal ion (eg, lithium ion, sodium ion). Potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidinium ions, tetramethylphosphonium).

[ink]
The ink of the present invention includes at least a polymer aqueous dispersion having a structure derived from a dye and a pigment.
The ink of the present invention is preferably used for inkjet printing.
Hereinafter, each component will be described.

(Polymer having structure derived from 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 means one or more arbitrary hydrogen atoms from an organic compound used as a dye. A group formed by removing (dye residue), preferably 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. In the case of a linear polymer, the structure derived from the dye may be included in the main chain of the polymer, or may be included in the side chain.
The dye polymer is preferably a polymer having a repeating unit containing a structure derived from a dye.
The method for obtaining the dye polymer is arbitrary, but a method for obtaining a dye polymer by polymerizing or copolymerizing a monomer containing a structure derived from a dye, or a polymer that does not have a structure derived from a dye in advance. Is prepared, and then a structure derived from a dye is introduced 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 a structure derived from a dye, a structure derived from a dye as classified by a color index (abbreviation “CI”), or an arbitrary substituent within the scope of the effect of the present invention in the structure A structure in which is substituted, or a structure in which an arbitrary substituent is removed from the structure within a range where the effects of the present invention are obtained is preferable.
Examples of structures derived from dyes include azo compounds (monoazo compounds, disazo compounds, trisazo compounds, polyazo compounds), stilbenes, carotenoids, diarylmethanes, triarylmethanes, xanthenes, acridines, quinolines, methines (monomethine, polymethine), A structure derived from any dye selected from azomethine, aniline, indoaniline, indamine, indophenol, azine, oxazine, thiazine, anthraquinone, indigo, quinophthalone, digrosine, porphyrin, dicyanostyryl compound, cyanine, and phthalocyanine Including.
The structure derived from the dye is azo compound, stilbene, diarylmethane, triarylmethane, xanthene, acridine, quinoline, polymethine, monomethine, azomethine, indoaniline, indophenol, nigrosine, oxazine, thiazine, anthraquinone, indigo, quinophthalone, porphyrin From the viewpoint of coloring power, an azo compound, stilbene, triarylmethane, xanthene, indoaniline, indophenol, nigrosine, anthraquinone, quinophthalone is preferable. More preferably, it includes a structure derived from any one of dyes selected from phthalocyanines, dicyanostyryl compounds, and phthalocyanines.

The dye may be a water-soluble dye or a water-insoluble dye, but it may be a water-insoluble dye from the viewpoint of water resistance and washing resistance of the dye polymer. preferable. Moreover, it is preferable that it is a dye which does not have ionic groups, such as a carboxyl group, a sulfo group, a phosphoric acid group, these salts, and an ammonium group. Such a dye is not particularly limited, and for example, a water-insoluble dye such as a disperse dye may be used, or a water-soluble dye obtained by removing an ionic group may be used.

As the dye polymer, a polymer containing a structure derived from a dye in the main chain or side chain is preferably used. The polymer constituting the main chain in the polymer containing a structure derived from a dye in the main chain or side chain is not particularly limited, but an acrylic polymer, urethane polymer (polyurethane), urea polymer (polyurea) or styrene polymer is preferably used. In particular, an acrylic polymer or a urethane polymer is preferable, and a urethane polymer is most preferable.
The acrylic polymer in the present invention is a polymer having at least one type of repeating unit from the group consisting of repeating units derived from (meth) acrylic acid and repeating units derived from (meth) acrylic acid esters. In this specification, “(meth) acrylic acid” represents at least one of acrylic acid and methacrylic acid, and “(meth) acrylic acid ester” represents at least one of acrylic acid ester and methacrylic acid ester. In addition, the urethane polymer in the present invention is a polymer having a urethane bond in the main chain, and includes a compound having two or more hydroxyl groups (polyol compound) and a compound having two or more isocyanate groups (polyisocyanate compound). Formed by reaction. The urethane polymer may be referred to as polyurethane. The urethane polymer in the present invention may further be a polymer having a urea bond. A polymer having a urethane bond and a urea bond is also referred to as “polyurethane / urea”. As one type of preferred form of the dye polymer in the present invention, there is a polyurethane / urea in which a structure derived from a dye and a first partial structure including a urethane bond and a second partial structure including a urethane bond are bonded by a urea bond. Can be mentioned. The urea polymer in the present invention is a polymer having a urea bond in the main chain, and is formed by a reaction between a compound having two or more amino groups (polyamine compound) and a polyisocyanate compound. The urea polymer is sometimes referred to as polyurea. Moreover, the styrene polymer in this invention means the polymer which has a repeating unit derived from styrene.
It is preferable that the dye polymer is polyurethane from the viewpoint of improving color developability. When the dye polymer is polyurethane, since the structure derived from the dye is not introduced into the side chain of the polymer but introduced into the main chain, the structure derived from the dye is less likely to aggregate and the color developability is improved. I guess.

The structure derived from the dye in the dye polymer is not limited as long as the effect of the present invention is achieved, but an arbitrary hydrogen atom from the dye represented by any one of the following general formulas (M1) to (M9) is 1 The dye residue is preferably one or more (preferably one or two) removed, and is represented by any one of the following general formulas (M1) to (M3), (M5), (M7) to (M9). More preferably, it is a dye residue obtained by removing one or more (preferably one or two) arbitrary hydrogen atoms from the dye. In addition, general formula (M2) and (M3) shall also include each resonance structure.

In general formula (M1), R ¹⁰¹ to R ¹¹⁰ each independently represents a hydrogen atom or a substituent.
In general formula (M2), R ²⁰¹ to R ²¹⁵ each independently represent a hydrogen atom or a substituent, X ²⁰¹ represents a monovalent anion, and n201 represents 0 or 1.
In general formula (M3), R ³⁰¹ to R ³¹⁷ each independently represent a hydrogen atom or a substituent, X ³⁰¹ represents a monovalent anion, and n301 represents 0 or 1.
In General Formula (M4), R ⁴⁰² to R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent, Ar ⁴⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group, and the phenyl group, the naphthyl group, or The heterocyclic group may further have a substituent.
In general formula (M5), R ⁵⁰¹ to R ⁵⁰⁸ each independently represent a hydrogen atom or a substituent.
In general formula (M6), R ⁶⁰¹ to R ⁶⁰² each independently represents a hydrogen atom or a substituent, R ⁶⁰³ represents a hydrogen atom or a substituent, and Ar ⁶⁰¹ represents a phenyl group, a naphthyl group, or a heterocyclic group. And the phenyl group, the naphthyl group, or the heterocyclic group may further have a substituent.
In general formula (M7), R ⁷⁰¹ to R ⁷⁰⁶ each independently represent a hydrogen atom or a substituent.
In general formula (M8), R ⁸¹¹ to R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ each independently represent a hydrogen atom or a substituent.
In general formula (M9), R ¹ to R ¹⁸ each independently represents a hydrogen atom or a substituent. R ¹⁹ and R ²⁰ each independently represents an alkyl group or a hydroxyalkyl group.

R ¹⁰¹ to R ¹¹⁰ in general formula (M1), R ²⁰¹ to R ²¹⁵ in general formula (M2), R ³⁰¹ to R ³¹⁷ in general formula (M3), R ⁴⁰² to R in general formula (M4) ⁴⁰⁷ , R ⁵⁰¹ to R ⁵⁰⁸ in general formula (M5), R ⁶⁰¹ to R ⁶⁰³ in general formula (M6), R ⁷⁰¹ to R ⁷⁰⁶ in general formula (M7), R ⁸¹¹ in general formula (M8) To R ⁸¹⁸ and R ⁸²¹ to R ⁸²⁸ , and when R ¹ to R ^{18 in} formula (M9) represent a substituent, the substituent is selected from the substituent group A (preferably the substituent described above) Substituents selected from group A1).

R ¹⁰¹ to R ¹¹⁰ in general formula (M1), R ²⁰¹ to R ²¹⁵ in general formula (M2), R ³⁰¹ to R ³¹⁷ in general formula (M3), R ⁴⁰² to R in general formula (M4) ⁴⁰⁷ , when R ⁵⁰¹ to R ⁵⁰⁸ in the general formula (M5) and R ⁶⁰¹ to R ⁶⁰² in the general formula (M6) represent a substituent, at least two of the substituents are bonded to each other, and It may form a 6-membered, 6-membered, or 7-membered saturated or unsaturated ring. When the formed 5-membered, 6-membered, and 7-membered rings are further substitutable groups, they may further have a substituent, and the substituent is selected from the above substituent group A. (Preferably a substituent selected from the above substituent group A1).

The substituent in the case where Ar ⁴⁰¹ in the general formula (M4) further has a substituent and the substituent in the case where Ar ⁶⁰¹ in the general formula (M6) further has a substituent are selected from the above substituent group A. And a substituent (preferably a substituent selected from the substituent group A1).

X ²⁰¹ in the general formula (M2) and X ³⁰¹ in the general formula (M3) are preferably chlorine ion, acetate ion, triflate ion, tetrafluoroborate ion, tetrakis (pentafluorophenyl) borate ion, perchlorate ion, or Bis (trifluoromethanesulfonyl) imide anion is preferred.

Some of the dyes represented by the general formulas (M1) to (M9) are classified by color index, and can be synthesized by a conventionally known method (for example, Japanese Patent Publication No. 7-49583, patent) No. 5715380, International Publication No. 2010/110199, Japanese Translation of PCT International Publication No. 2002-509957, etc.).

Specific examples of the dyes represented by the general formulas (M1) to (M9) are those described in [0126] to [0132] of International Publication No. 2017/131107, and [0092] of Japanese Patent Application No. 2017-034066. ] To [0100] and those described in [0068] of JP 2013-535558 A can be referred to.

(Molecular weight of dye polymer)
When the dye polymer does not have a crosslinked structure, the weight average molecular weight (Mw) of the dye polymer is preferably 3,000 to 2,000,000, more preferably 3,000 to 1,000,000, and 3,000 to 200,000 is particularly preferred. The weight average molecular weight of the dye polymer can be measured by gel permeation chromatography (GPC).

(Structure of dye polymer)
The dye polymer may have a structure derived from a dye as an essential structure, but it is preferable to introduce a dispersing group from the viewpoint of dispersibility in water. The dispersing group may be ionic or nonionic. At least one of a hydrophobic group (an electrically neutral non-polar group having low affinity with water) and an ionic group (an electrically ionic polar group having high affinity with water) Repeating units containing may be introduced.
The molecular structure of the dye polymer may be linear or branched, may be random, alternating, periodic, or block, and may be a graft polymer designed with a trunk and branch structure.

The dye polymer may have a structure having an ionic group as a dispersing group. The introduction amount of the structure having an ionic group in the dye polymer is preferably such that the acid value or amine value of the dye polymer is 1 to 60 mgKOH / g, and is preferably 1 to 30 mgKOH / g. More preferably. Within the above range, the dispersion stability and wash fastness of the aqueous dispersion of the dye polymer 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 dye polymer 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 the dye polymer are excellent.
The dye polymer preferably has an anionic group.
The anionic group is preferably an acid group.

The dye polymer preferably has a crosslinked structure. By having a crosslinked structure, the strength of the film formed by fusing the dye polymer 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 (manufactured by Wako Pure Chemical Industries, Aldrich or Tosoh Corporation), duranate (manufactured by Asahi Kasei Corporation, trade name), and the like.
In general, since a polymer having a crosslinked structure is hardly soluble in an organic solvent, when a dye polymer is mixed with dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), or tetrahydrofuran (THF), it is insoluble in any solvent. If the minute remains, it can be considered that the dye polymer is a polymer having a crosslinked structure.

As will be described later, in the inkjet printing method of the present invention, it is preferable to perform a heat treatment step after printing an aqueous dispersion of a dye polymer. In the heat treatment step, since the dye polymer is melt-dyed, the dye polymer is preferably melted at a heat treatment temperature or lower. Since the heat treatment step is preferably performed at 100 to 200 ° C., the dye polymer is preferably melted at 200 ° C. or less, and more preferably at 180 ° C. or less.
The Tg (glass transition temperature) of the dye polymer is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and even more preferably 150 ° C. or lower.
The Tg of the dye polymer can be measured by DSC (differential scanning calorimetry).
The dye polymer has a higher Tg by having a structure derived from a dye as compared with a polymer not having a structure derived from a dye. In the acrylic polymer in which the structure derived from the dye is introduced into the side chain of the (meth) acrylate ester, it may not melt at 200 ° C. depending on the structure or composition, but the main chain is polyurethane, and the main chain or side chain A polymer having a structure derived from a dye often melts at 200 ° C. or lower.

(Aqueous dispersion of dye polymer)
The aqueous dispersion of dye polymer (dye polymer aqueous dispersion) contains at least water and the dye polymer, and may further 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).
The dye polymer can be used alone or in admixture of two or more.

In the present invention, the above-described dye polymer is used not in a state dissolved in water but in a state dispersed in water (water dispersion).
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 insoluble 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 particulate 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 in the dye polymer aqueous dispersion is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 3 to 25% by mass. Within this range, a high-density colored cloth can be obtained in printing while ensuring storage stability as an inkjet ink.
The water content in the dye polymer aqueous dispersion is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. This range is preferable because the stability of the aqueous dispersion and the ejection stability as an inkjet ink can be imparted. The stability of the aqueous dispersion indicates that precipitation or the like hardly occurs.

(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% by mass 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. Is preferably adjusted arbitrarily.

The content of the polymeric dispersant is preferably in the range of 0.001% by mass 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 this range. It is preferable to adjust to. *

The method for producing an aqueous dispersion of a dye polymer is as follows:
(I) After mixing a dye polymer powder or paste and, if necessary, a low molecular surfactant or a high molecular dispersant in water or an aqueous organic solvent, glass beads, zirconia beads, titania beads, Or a method of finely dispersing with an attritor or a mill with stainless steel balls,
(Ii) a method of obtaining an aqueous dispersion of a dye polymer by synthesizing a dye polymer in an organic solvent and then adding water, optionally a surfactant or a solvent, and removing a solvent other than water;
(Iii) An organic solvent, a compound having a structure derived from a dye and having a group that reacts with a polyisocyanate compound, a polyisocyanate compound, and other monomers and a polymerization initiator as necessary are added. In addition, a compound having a structure derived from a dye in an organic solvent and having a group that reacts with a polyisocyanate compound is polymerized, and water, optionally a neutralizer, an emulsifier (surfactant), and a chain extender are added. Emulsifying and chain-extending the polymer, and then appropriately removing the organic solvent to obtain an aqueous dispersion of the dye polymer,
(Iv) An organic solvent solution of a first prepolymer having an isocyanate group at the terminal, obtained by reacting a compound having a structure derived from a dye and having a group that reacts with a polyisocyanate compound and the polyisocyanate compound An organic solvent solution of a second prepolymer having a dispersible structure and having an isocyanate group at the terminal, optionally mixed with an emulsifier (surfactant) and an organic solvent, water, optionally an emulsifier (surfactant) And the like, and an organic solvent is appropriately removed to obtain an aqueous dispersion of a dye polymer. These can be suitably used.

[Pigment]
The ink of the present invention contains a pigment.
The pigment is not particularly limited,
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 selected from

In the present invention, an aqueous pigment dispersion (also referred to as a “pigment aqueous dispersion”) in which a pigment is dispersed in water using a dispersant may be used in preparing the ink. As the pigment aqueous dispersion, the pigment dispersion described in JP2012-7148A can be used.

As the pigment, a self-dispersing pigment can also be used. Self-dispersing pigments that can be used include self-dispersing carbon black CAB-O-JET 200, 300 (above, manufactured by Cabot), BONJET CW-1 (500 μmol / g as a carboxy group), CW-2 ( Commercially available products such as carboxy group (470 μmol / g) (manufactured by Orient Chemical Co., Ltd.), Tokai Carbon Co., Ltd. Aqua-Black 162 (carboxyl group: about 800 μmol / g), and the like.
A pigment can be used individually or in mixture of 2 or more types in arbitrary ratios.
In the present invention, the dye polymer can also be used as a dispersant for dispersing the pigment in water. However, when a dye polymer is used as a pigment dispersant, the dye polymer present as a dispersant around the pigment is not the “aqueous dispersion of dye polymer” in the present invention. That is, the “dye polymer aqueous dispersion” in the present invention does not contain a pigment. Accordingly, the ink of the present invention includes a pigment dispersion containing a pigment and a dye polymer that exists as a dispersant around the pigment, even when a dye polymer is used as the pigment dispersant. And an aqueous dispersion of the polymer. An ink containing a pigment dispersion that does not contain an aqueous dispersion of a dye polymer but includes a pigment and a dye polymer that exists as a dispersant around the pigment is a heat treatment step in inkjet printing, and the dye polymer is converted into a pigment by melting the dye polymer. May peel off and the pigment may bleed out.

(Aqueous organic solvent)
The aqueous organic solvent preferably has a water solubility of 10 g / 100 g-H ₂ O or more at 25 ° C., more preferably 20 g / 100 g-H ₂ O or more, and is 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 dye polymer aqueous dispersion 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 and the ejection stability as an inkjet ink can be imparted.

(Crosslinking agent)
The ink of the present invention may contain a cross-linking agent for the purpose of improving the friction resistance or washing fastness of the colored fabric. 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).

The ink of the present invention contains at least a water dispersion of a dye polymer and a pigment. That is, the ink of the present invention is a dispersion in which a dye polymer and a pigment are dispersed in a liquid containing water. The dye polymer is in the form of particles in the ink of the present invention, and the preferred average particle size of the particulate dye polymer is the same as described above.
The content of the dye polymer in the ink of the present invention is preferably from 0.1 to 20% by mass, more preferably from 1 to 15% by mass, and even more preferably from 3 to 12% by mass.
The pigment content in the ink of the present invention is preferably 0.5 to 30% by mass, more preferably 1.0 to 15% by mass. If the addition amount of the pigment is 0.5% by mass or more, the printing density is preferably increased, and if it is 30% by mass or less, the viscosity of the ink is increased or the structural property is hardly generated in the viscosity characteristic. This is preferable because of excellent discharge stability.
The water content in the ink for ink jet textile printing of the present invention is preferably 20 to 95% by mass, and more preferably 50 to 90% by mass.
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, an aqueous dispersion of a pigment, and, if necessary, water or other components. .

(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 adjusting agent 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.

(Aqueous dispersion of water-insoluble polymer without structure derived from dye)
The ink of the present invention may further contain an aqueous dispersion of a water-insoluble polymer having no structure derived from a dye, in addition to the aqueous dispersion of a polymer having a structure derived from the dye and the pigment.
By further including an aqueous dispersion of a water-insoluble polymer that does not have a structure derived from a dye in the ink of the present invention, the dye polymer and / or the pigment can be firmly fixed to the fabric in inkjet printing.
In the present invention, the water-insoluble polymer is a polymer that is dispersed as particles in water at 25 ° C. The average particle size (MV) of the water dispersion of the water-insoluble polymer is preferably 50 to 500 nm, preferably 20 to 500 nm, and more preferably 30 to 300 nm. If the polymer is dissolved in water, the polymer is not present as particles in water.
The water-insoluble polymer that does not have a structure derived from a dye is a polymer that does not have a structure derived from a dye in the molecule, and the “structure derived from a dye” is as described above.
The water-insoluble polymer having no structure derived from a dye is preferably a colorless polymer.

An aqueous dispersion of a water-insoluble polymer not having a structure derived from a dye contains at least water and a water-insoluble polymer not having a structure derived from a dye, and water having no structure derived from a dye. The insoluble polymer is dispersed in water. In addition, the water-insoluble polymer which does not have the structure derived from a dye is a component different from the polymer dispersing agent which can be used as a dispersing agent. A water-insoluble polymer that does not have a structure derived from a dye exists by being dispersed alone in the ink, while a polymer dispersant is dispersed in a mixture with an aqueous dispersion of a dye polymer in the ink. Exist.
The water-insoluble polymer having no structure derived from a dye is preferably polyurethane, polyester, acrylic polymer, styrene-butadiene copolymer, or polyvinyl chloride. The water-insoluble polymer having no structure derived from the dye may be used alone or in combination of two or more.
A water-insoluble polymer having no structure derived from a dye may be synthesized by a known method, or a commercially available product may be used.
Specific examples of polyurethane that can be used as a water-insoluble polymer that does not have a structure derived from a dye include Takelac manufactured by Mitsui Chemicals, Inc., Elastron manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Taisei Fine Chemical Co., Ltd. The WBR series, Meisei Chemical Industry Co., Ltd. pass call, Enomoto Kasei Co., Ltd. Neorez series, etc. are mentioned.
Specific examples of the polyester that can be used as a water-insoluble polymer that does not have a structure derived from a dye include Toyobo Co., Ltd. vylonal, Takamatsu Yushi Co., Ltd. pesresin, and the like.
Specific examples of the acrylic polymer that can be used as a water-insoluble polymer that does not have a structure derived from a dye include styrene / acrylic resin from Nippon Synthetic Chemical Co., Ltd., Movinyl series, and Lovene series from Mallard Creek Polymers. Styrene / acrylic resin, acrylic resin, and urethane / acrylic resin.
Examples of the styrene-butadiene copolymer that can be used as a water-insoluble polymer having no structure derived from a dye include the Loveven series manufactured by Mallard Creek Polymers, and Nipol Lx421 manufactured by Nippon Zeon Co., Ltd.
Specific examples of polyvinyl chloride that can be used as a water-insoluble polymer that does not have a structure derived from a dye include vinibran manufactured by Nissin Chemical Industry Co., Ltd.

As will be described later, in the inkjet printing method of the present invention, it is preferable to perform a heat treatment step after printing the ink. In the heat treatment step, the water-insoluble polymer that does not have a structure derived from a dye is preferably melted at a heat treatment temperature or lower as in the above-described dye polymer. A water dispersion of a water-insoluble polymer having no structure derived from a dye melts at a temperature lower than the heat treatment temperature, whereby the dye polymer and / or the pigment can be firmly fixed on the fabric. Since the heat treatment step is preferably performed at 100 to 200 ° C., the water-insoluble polymer having no structure derived from the dye is preferably melted at 200 ° C. or less, more preferably 180 ° C. or less.
The Tg (glass transition temperature) of the water-insoluble polymer having no structure derived from the dye is preferably 200 ° C. or less, more preferably 180 ° C. or less, and further preferably 150 ° C. or less.
The Tg of a water-insoluble polymer having no structure derived from a dye can be measured by DSC (differential scanning calorimetry).
From the reason of maintaining a good texture of the colored fabric when the ink of the present invention is used for inkjet printing, it is even more preferable that the Tg of the water-insoluble polymer having no structure derived from the dye is 150 ° C. or less. It is particularly preferably 120 ° C. or less, and most preferably less than 100 ° C. The lower the Tg of the water-insoluble polymer that does not have a structure derived from a dye, the softer the resulting film, the better the texture of the colored cloth.

The content of the water-insoluble polymer having no structure derived from the dye in the aqueous dispersion of the water-insoluble polymer having no structure derived from the dye is preferably 0.1 to 40% by mass, more preferably The content is 1 to 30% by mass, and particularly preferably 1 to 25% by mass.
The water content in the aqueous dispersion of the water-insoluble polymer having no structure derived from the dye is preferably 40 to 95% by mass, more preferably 50 to 90% by mass.

When the ink of the present invention contains an aqueous dispersion of a water-insoluble polymer that does not have a structure derived from a dye, the aqueous dispersion of a water-insoluble polymer that does not have a structure derived from a dye in the ink of the present invention The amount is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 15% by weight.

For matters other than those described above, the water-insoluble polymer and dye having no structure derived from the dye except that the structure derived from the dye does not have a preferable range of Tg is the above range. The detailed description of the aqueous dispersion of the water-insoluble polymer having no derived structure is the same as that described above for the dye polymer and the aqueous dispersion of the dye polymer.

[Other ingredients]
The ink of the present invention may contain other components other than those described above. Other components include, for example, colorants other than the above dye polymers and pigments, organic solvents, surfactants, fluorescent brighteners, surface tension modifiers, antifoaming agents, drying inhibitors, lubricants, thickeners, Examples include ultraviolet absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, specific resistance adjusting agents, rust inhibitors, inorganic pigments, anti-reducing agents, antiseptics, antifungal agents, and chelating agents.

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. In addition, when the ink of the present invention 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 adjusted to 20 mPa · s or less. It is particularly preferred. Viscosity is measured using an E-type rotational viscometer, controlled at 25 ° C.
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 color of the ink of the present invention is not particularly limited. For example, yellow ink, cyan ink, magenta ink, and black ink are preferable.
When the ink of the present invention is a black ink, it is preferable because it is excellent in the effect of tightening other colors. In recent years, high density black ink has been demanded in the textile industry. Dark black is in demand because it has the effect of producing a high-class feeling and the effect of tightening other colors. On the other hand, in printing, unlike printing on paper, which is a substrate that does not transmit light, it is difficult to print at a high density because the object to be printed is a fabric (particularly a woven fabric) that is a substrate that transmits light. Further, it is known that in printing on paper, the density can be improved by devising an image receiving layer such as coated paper.
Also, in screen printing, etc., it can be dyed to dark black by sufficiently dyeing it using a large amount of colored glue, but in ink jet printing, the amount of droplet ejection is limited, and it is difficult to express dark black. There's a problem.

[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 the ink of the present invention on a fabric by an ink jet method, and there are the following two preferred embodiments.
1st aspect: The inkjet printing method which has the process of printing the ink of this invention directly on a fabric by an inkjet system.
Second aspect: A pretreatment step in which an aqueous pretreatment liquid containing a flocculant is applied to a fabric to obtain a pretreated fabric, and the ink of the present invention is directly printed on the fabric pretreated by an inkjet method. An ink jet textile printing method comprising the step of:
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 an effect of 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 flocculant is a cationic compound or a polyvalent metal salt and the dye polymer has an anionic group (preferably an acid group), a high-concentration colored cloth is obtained by printing with the ink jet printing method. be able to. 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 dye polymer having an anionic group, resulting in the surface. It is thought that the amount of the dye polymer present increases and the concentration can 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 compounds such as polyallylamine or derivatives thereof, amine-epihalohydrin copolymers, or other quaternary ammonium salt type cationic polymers. Examples include charged cationic polymers. In some cases, a water-dispersible cationic polymer can 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.

As will be described later, the ink jet textile printing method of the present invention is further integrated with the fiber by further adding a heat treatment step, so that the dye polymer is fused to the fiber of the fabric, and further imparts friction resistance and the like. There is an advantage that you can.

(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). Can do). The colored fabric is preferably dried and then heat treated for the purpose of melt dyeing, usually at 100 to 250 ° C., more preferably at 100 ° C. to 200 ° C., particularly preferably at 120 ° C. to 200 ° C. The heat treatment time is preferably 30 seconds to 3 minutes. When a reactive group (for example, a blocked isocyanate group) is introduced into the dye polymer, or when a crosslinking agent (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent) is used as an additive, From the viewpoint of friction resistance, it is possible to cause a crosslinking reaction using a reactive group introduced into the polymer (for example, a blocked isocyanate group) or a crosslinking agent used in combination as an additive (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent). preferable.

(Post-processing)
The fabric colored by the inkjet printing method of the present invention (colored fabric) is excellent in fastness (friction resistance). However, if necessary, the fabric can be fastened by padding the entire surface with a post-treatment agent (if necessary). In particular, it is possible to obtain a colored cloth having further improved friction resistance. Post-treatment agents for the purpose of softening include cationic surfactants, anionic surfactants, nonionic surfactants, dimethyl silicone oil, amino silicone oil, carboxy modified silicone oil, hydroxy modified silicone oil, fatty acid , Fatty acid amide, mineral oil, vegetable oil, animal oil, plasticizer and the like.
Further, as a post-treatment agent for improving the smoothness of the colored fabric surface, metal soap, paraffin wax, carnauba wax, microstalline wax, dimethyl silicone oil, amino silicone oil, carboxy modified silicone oil, hydroxy modified silicone oil, etc. Is mentioned.
In the padding treatment, these post-treatment agents are emulsified, thermally emulsified, or dispersed in a water solvent by stirring with a mixer, and a colored cloth is dipped, dried with mangles, dried and heat treated.
Moreover, the friction resistance of a colored cloth can be improved by mix | blending a small amount of resin emulsion as a fixing agent in a post-processing agent. The blending amount with respect to the post-treatment agent is preferably less than 5%, which is preferable because the softness of the texture of the colored fabric is not easily impaired.
The resin emulsion blended into the post-treatment agent as a sticking agent is not particularly limited, but is an acrylic ester resin emulsion, a urethane resin emulsion, an ethylene / vinyl acetate copolymer resin (EVA resin) emulsion, a silicone / acrylic resin emulsion. Polyester resin emulsions and the like can be used, and in order to soften the texture of the colored cloth, the glass transition point of these resin emulsions is preferably 0 ° C. or lower.

(Fabric)
Examples of 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, non-woven fabrics, etc. Is 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 dye polymer, 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 and an ink jet printer having the ink of the present invention.

[Colored fabric]
The present invention also relates to a colored fabric comprising a fabric, a dye polymer, and a pigment. The fabric, the dye polymer, and the pigment are as described above.
The colored fabric of the present invention can be produced by the above-described inkjet printing method of the present invention.

[Synthesis of Dye Polymer (Y-2-1)]
The dye polymer (Y-2-1) was synthesized according to the following scheme. The unit of the ratio of the following repeating units is mass%.

10 mL of N-methylpyrrolidone (NMP) was added to a 100 mL three-necked flask, and the internal temperature was raised to 85 ° C. In the NMP, 9.0 g of a polymerizable monomer YM-1 (synthesized by the method described in Japanese Patent No. 5315267), 1.0 g of a polymerizable monomer methacrylic acid (MAA), V-601 (manufactured by Wako Pure Chemical Industries, Ltd., Trade name) 0.126 g and a solution prepared by dissolving 0.443 g of 1-dodecanethiol in 13.24 g of NMP was added dropwise over 3 hours. After completion of dropping, the reaction solution A was obtained by reacting at 85 ° C. for 1 hour. Thereafter, V-601 (0.098 g) was added to the reaction solution A, and the mixture was further reacted at 85 ° C. for 2 hours to obtain a reaction solution B. The reaction solution B is allowed to cool to 20 ° C., poured into 500 mL of water, crystals are precipitated, the crystals are filtered off, and the filtered crystals are dried in a 60 ° C. air dryer for one day to obtain a dye polymer. A yellow powder of (Y-2-1) was obtained. The yield of the dye polymer (Y-2-1) was 8.7 g. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of the dye polymer (Y-2-1) in tetrahydrofuran (THF) was 441 nm. The weight average molecular weight (Mw) of the dye polymer (Y-2-1) measured by gel permeation chromatography (GPC) is 10,500 (in terms of polystyrene), and the dispersity (Mw / Mn) is 1.7. Met. The weight average molecular weight of the dye polymer was calculated from gel permeation chromatography (GPC) measurement. Specifically, HLC-8220GPC (manufactured by Tosoh Corporation) was used.

[Synthesis of Dye Polymer (Br-1)]
According to Example 1 of JP-T-2002-509957, a polyurethane compound (Br-1) as a dye polymer was synthesized.

[Synthesis of Dye Polymer (B-5)]
According to Example 11 of JP-T-2002-509957, a polyurethane compound (B-5) as a dye polymer was synthesized.

[Synthesis of Dye Polymer (D-3-2)]
The dye polymer (D-3-2) was synthesized according to the following scheme. The unit of the ratio of the following repeating units is mass%.

To a 200 mL three-necked flask, 5.0 g of D-3, 0.79 g of 2,2-bis (hydroxymethyl) propionic acid and 45.8 g of N-methylpyrrolidone (NMP) were added, and the internal temperature was raised to 90 ° C. . To this, 81 mg of Neostan U-600 (manufactured by Nitto Kasei, trade name) and 2.46 g of isophorone diisocyanate were added. After completion of the dropwise addition, the mixture was reacted at 90 ° C. for 4 hours. The reaction solution was allowed to cool to 20 ° C., poured into 1 L of a 0.1 mol / L aqueous sodium hydroxide solution, 110 mL of 1 mol / L aqueous hydrochloric acid was added, and the mixture was filtered. The obtained residue was added to 1 L of a 0.1 mol / L aqueous sodium hydroxide solution and stirred for 10 minutes. Then, 1 mol / L aqueous hydrochloric acid was added to adjust the pH to 5.2, followed by filtration. The obtained residue was poured into 500 mL of water, stirred for 10 minutes, and then filtered. The obtained residue was dried with a vacuum dryer at 60 ° C. for 3 hours to obtain a dye polymer (D-3-2). Yield 23.2 g. The dye polymer (D-3-2) had an absorption maximum wavelength of 555 nm in an ultraviolet-visible absorption spectrum in a dilute solution of methanol / chloroform = 1/1. Moreover, the weight average molecular weight (Mw) in GPC measurement was 13,100 (polymethylmethacrylate conversion), and dispersion degree (Mw / Mn) was 4.3. As GPC, HLC-8220 GPC (manufactured by Tosoh Corporation) was used.

[Preparation of dye polymer aqueous dispersion (Y1)]
1.0 g of dye polymer (Y-2-1), 10 g of zirconia beads (made by Nikkato, trade name YTZ ball, diameter 0.1 μm), 0.3 g of 10% by weight aqueous solution of sodium oleate, and 3.7 g of ultrapure water In addition, the mixture was dispersed for 8 hours at a rotation speed of 400 rpm (revolution per minute) using a planetary fine pulverizer (Pulverset 7 manufactured by Fritsch). From the obtained dispersion, zirconia beads were removed using a filter cloth to obtain a dye polymer aqueous dispersion (Y1). The average particle diameter (MV) of the particulate dye polymer in the dye polymer aqueous dispersion (Y1) was 160 nm.

[Preparation of dye polymer aqueous dispersion (Bk1)]
Add 1.0 g of dye polymer (Br-1), 1.0 g of dye polymer (B-5), 20 g of zirconia beads (product name: YTZ ball, diameter 0.1 μm), and 8.0 g of ultrapure water. Using a planetary fine pulverizer (Pulversette 7 manufactured by Fritsch), the mixture was dispersed for 5 hours at a rotation speed of 400 rpm (revolution per minute). From the obtained dispersion, zirconia beads were removed using a filter cloth to obtain a dye polymer aqueous dispersion (Bk1). The average particle diameter (MV) of the particulate dye polymer in the dye polymer aqueous dispersion (Bk1) was 190 nm.

[Preparation of dye polymer aqueous dispersion (M1)]
A dye polymer aqueous dispersion (M1) was prepared in the same manner as the dye polymer aqueous dispersion (Y1) except that the dye polymer (D-3-2) was used in place of the dye polymer (Y-2-1). It was created. The average particle diameter (MV) of the particulate dye polymer in the dye polymer aqueous dispersion (M1) was 130 nm.

[Preparation of pigment dispersion (Y2)]
A styrene-acrylic acid copolymer (Johncrill 678, manufactured by BASF, trade name) 3 g, dimethylaminoethanol 1.3 g, and ion-exchanged water 80.7 g were stirred at 70 ° C. and mixed. Next, C.I. I. 15 g of Pigment Yellow 180 and 50% by volume of zirconia beads having a particle diameter of 0.5 mm were filled by volume and dispersed using a sand grinder mill to obtain a pigment dispersion (Y2) having a pigment content of 15% by mass. .

[Preparation of pigment dispersion (Bk2)]
C. I. A pigment dispersion (Bk2) was prepared in the same manner as the pigment dispersion (Y2) except that carbon black was used instead of Pigment Yellow 180.

[Preparation of pigment dispersion (M2)]
C. I. Pigment Yellow 180 instead of C.I. I. A pigment dispersion (M2) was prepared in the same manner as the pigment dispersion (Y2) except that CI Pigment Red 122 was used.

[Preparation of pigment dispersion (C2)]
C. I. Pigment Yellow 180 instead of C.I. I. A pigment dispersion (C2) was prepared in the same manner as the pigment dispersion (Y2) except that CI Pigment Blue 15: 3 was used.

Example 1
[Creation of yellow ink 1]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a membrane filter (average pore size 0.8 μm) to prepare Yellow Ink 1.
Dye polymer aqueous dispersion (Y1) 2.0 g
1.0 g of pigment dispersion (Y2)
Trimethylolpropane 0.056g
0.913g of ultrapure water
1,12-hexanediol 0.112g
Glycerin 0.560g
Triethylene glycol monobutyl ether 0.112 g
2-pyrrolidone 0.168g
Propylene glycol 0.028g
Surfynol 465 (trade name, manufactured by Nissin Chemical Industry) 0.056g

[Inkjet printing]
Yellow ink 1 is loaded into an ink cartridge as ink for ink-jet textile printing, and polyester fabric (polyester tropical (manufactured by Teijin Limited), Inc. Color dyeing, product code A02-01019), cotton fabric (with cotton broad sill, color dyeing, product code A02-01002), and polyester 65% cotton 35% blend (blend polyester 65 / cotton 35 broad) The images were printed on the product code A02-01030) manufactured by Color Dye Co., Ltd. and dried at 20 ° C. for 12 hours. After drying, heat treatment was performed using a heat press (Asahi Textile Machinery Co., Ltd., trade name: tabletop automatic flat press AF-54TEN type) at a temperature of 200 ° C., a pressure of 0.20 N / cm ² , and a time of 60 seconds. A colored fabric was obtained.

(Comparative Example 1)
[Creation of yellow ink 2]
(Preparation of aqueous binder)
50 g of 2-butanone was placed in a three-necked flask, and the internal temperature was raised 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 for 3 hours. It was dripped over. After dropping, the mixture was heated to reflux for 5 hours, cooled to 20 ° C., and heated under reduced pressure to obtain a polymer residue. To this, 350 mL of ion-exchanged water and 1.05 times moles of sodium hydroxide of acrylic acid added as a monomer were added and dissolved. It diluted with ion-exchange water so that the whole quantity might be 500g, and obtained the 20 mass% aqueous solution of the aqueous | water-based binder.

(Preparation of pigment ink)
46.6 g of the pigment dispersion (Y2), 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 , 11.2 g of diethylene glycol and 0.6 g of Olfine 465 (manufactured by Nissin Chemical Industry Co., Ltd.) are mixed, and ion-exchanged water is added thereto to make a total amount of 100 g, followed by filtration through a 0.8 μm filter. Ink 2 was obtained.

[Inkjet printing]
Ink-jet printing was performed in the same manner as in Example 1 except that the yellow ink 2 was used in place of the yellow ink 1 to obtain a colored fabric.

(Example 2)
[Create Black Ink 1]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a membrane filter (average pore size 0.8 μm) to prepare Black Ink 1.
Dye polymer aqueous dispersion (Bk1) 2.0 g
Pigment dispersion (Bk2) 2.0g
Trimethylolpropane 0.056g
0.913g of ultrapure water
1,12-hexanediol 0.112g
Glycerin 0.560g
Triethylene glycol monobutyl ether 0.112 g
2-pyrrolidone 0.168g
Propylene glycol 0.028g
Surfynol 465 (trade name, manufactured by Nissin Chemical Industry) 0.056g

[Inkjet printing]
Ink-jet printing was performed in the same manner as in Example 1 except that the black ink 1 was used in place of the yellow ink 1 to obtain a colored fabric.

(Comparative Example 2)
[Create Black Ink 2]
A black ink 2 was prepared in the same manner as the yellow ink 2 except that the pigment dispersion liquid (Bk2) was used instead of the pigment dispersion liquid (Y2).

[Inkjet printing]
Ink-jet printing was performed in the same manner as in Example 1 except that the black ink 2 was used in place of the yellow ink 1 to obtain a colored fabric.

(Example 3)
[Magenta ink 1 creation]
Similar to the preparation of yellow ink 1 except that the dye polymer aqueous dispersion (M1) was used instead of the dye polymer aqueous dispersion (Y1) and the pigment dispersion (M2) was used instead of the pigment dispersion (Y2). Thus, magenta ink 1 was prepared.

[Inkjet printing]
Ink-jet printing was performed in the same manner as in Example 1 except that magenta ink 1 was used in place of yellow ink 1, and a colored fabric was obtained.

(Comparative Example 3)
[Magenta ink 2 creation]
A magenta ink 2 was prepared in the same manner as the yellow ink 2 except that the pigment dispersion liquid (M2) was used instead of the pigment dispersion liquid (Y2).

[Inkjet printing]
Ink-jet printing was performed in the same manner as in Example 1 except that magenta ink 2 was used in place of yellow ink 1, and a colored fabric was obtained.

Example 4
[Preparation of aqueous pretreatment liquid A (1) containing flocculant]
An aqueous pretreatment liquid A (1) was prepared by mixing and stirring the following components. Cathiomaster PD-7 contains a cationic compound as a flocculant.
Cachio Master PD-7 (Yokkaichi Synthesis, solid content 50% by mass) 50g
BYK348 (by Big Chemie Japan) 5g
Glycerin 100g
845g of water

[Pretreatment process]
Polyester fabric (polyester tropical (manufactured by Teijin Ltd.), Color dye Co., Ltd., product code A02-01019), cotton fabric (with cotton broad sill, product of color dye Co., Ltd., product code A02-01002), and polyester 65% cotton 35% blend (mixed polyester 65 / cotton 35 broad, manufactured by Color Dyeing Co., Ltd., product code A02-01030) was applied with the aqueous pretreatment liquid A (1) prepared above by a padding method. It was squeezed at a squeezing rate of 70% and dried for 24 hours. The squeezing rate (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid relative to the fabric after the cloth containing the aqueous treatment liquid is squeezed.

[Inkjet printing process]
Ink-jet printing was carried out in the same manner as in Example 1 except that a pretreated fabric was used as a fabric to obtain a colored fabric.

(Example 5)
Ink-jet printing was performed in the same manner as in Example 4 except that the black ink 1 was used in place of the yellow ink 1 to obtain a colored cloth.

(Example 6)
Ink-jet printing was performed in the same manner as in Example 4 except that magenta ink 1 was used in place of yellow ink 1, and a colored fabric was obtained.

(Preparation of solution in which prepolymer 6 was dissolved in tetrahydrofuran)
In a three-necked flask, 4.5 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 13.6 parts by mass of the following phthalocyanine dye D-4, 25.3 parts by mass of tetrahydrofuran (THF), Neostan U-600 0.03 parts by mass (trade name, manufactured by Nitto Kasei Kogyo Co., Ltd.) was added and stirred at 65 ° C. for 4 hours. THF was added so that the final solid content concentration was 30% by mass, and a solution (prepolymer 6 solution) in which the prepolymer 6 was dissolved in THF was obtained. The prepolymer 6 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the terminal.
The following phthalocyanine dye D-4 was synthesized according to JP 2013-535558 A. From elemental analysis, it was m + n = 2 and p + q = 2. The prepolymer 6 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the terminal.

(Preparation of a solution in which prepolymer 4 is dissolved in THF)
In a three-necked flask, isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) 13.1 parts by mass, dimethylolbutanoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 4.0 parts by mass (equivalent to an acid value of 64 mgKOH / g), poly 6.4 parts by mass of caprolactone diol (manufactured by Aldrich, average molecular weight 530), 0.5 parts by mass of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 56.0 parts by mass of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) Part, 0.7 parts by mass of Neostan U-600 (trade name, manufactured by Nitto Kasei Kogyo Co., Ltd.) was added and stirred at 75 ° C. for 4 hours. Tetrahydrofuran was added so that the final solid content concentration would be 30% by mass, and filtered to obtain a solution in which the prepolymer 4 was dissolved in THF (prepolymer 4 solution). The prepolymer 4 is a polyurethane having a carboxyl group and a urethane bond and having an isocyanate group at the terminal.

(Preparation of aqueous dye polymer dispersion (ULx-7))
In a container, 17.6 parts by mass of the prepolymer 6 solution obtained above, 3.2 parts by mass of the prepolymer 4 solution, 10.4 parts by mass of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.), triethylamine ( 0.23 parts by mass of Wako Pure Chemical Industries, Ltd.) was added. Furthermore, a mixed liquid of 35.6 parts by mass of pure water and 11.7 parts by mass of a 4% by mass aqueous sodium dodecyl sulfate 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 parts by mass of a 10% by mass aqueous solution of UCAT SA102 (trade name, manufactured by San Apro Co., Ltd.) was added to the emulsified liquid, and pure water was added so that the solid content concentration was 15% by mass. And prepolymer 6 and prepolymer 4 were reacted for 2 days. Thereafter, coarse particles were removed by filtration to obtain 40 parts by mass of an aqueous dye polymer dispersion (ULx-7). The final solid content concentration of the dye polymer aqueous dispersion (ULx-7) was 14% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-7) was polyurethane / urea, and the average particle size (MV) thereof was 160 nm. In addition, the dye polymer was found to be a polymer having a crosslinked structure because insoluble matter remained in any of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF). It was.

(Example 7)
[Preparation of cyan ink 1]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare cyan ink 1.
Dye polymer aqueous dispersion (ULx-7) 3.0 parts by weight Pigment dispersion (C2) 1.0 part by weight Ultrapure water 5.18 parts by weight Glycerin 0.60 parts by weight Triethylene glycol monobutyl ether 0.12 parts by weight Surfynol 465 (trade name, manufactured by Nissin Chemical Industry) 0.10 parts by mass

[Inkjet printing]
The temperature of heat treatment using cyan ink 1 instead of yellow ink 1 as the ink for ink-jet textile printing and using a dried heat press (trade name: desktop automatic flat press machine AF-54TEN type, manufactured by Asahi Textile Machinery Co., Ltd.) Was changed to 180 ° C. instead of 200 ° C., inkjet printing was performed in the same manner as in Example 4 to obtain a colored fabric.

(Synthesis of dye monomer YM-1)
YM-1 was synthesized according to the following scheme.

In a three-necked flask, 333 g of Q-1 and 1 L of nitrobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 20 ° C. To the flask, 130 mL of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was washed with 300 mL of nitrobenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 90 ° C. for 10 hours. After cooling to 20 ° C., 1.3 L of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred, and the precipitate was collected by filtration to obtain Q-2. Q-2 was used directly in the next step. In a three-necked flask, 141 g of iminodiacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 420 mL of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), 1.8 L of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) are placed under ice cooling. Stir with. Q-2 was added to the flask, stirred for 30 minutes after the addition, and further stirred at 20 ° C. for 30 minutes. After stirring, 1.8 L of water was added, and the precipitate was collected by filtration to obtain Q-3. To a three-necked flask, 273 g of Q-3, 1.3 L of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) and 52 g of tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and maintained at 110 ° C. . 283 mL of 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 110 ° C. for 5 hours. After cooling to 20 ° C., 3.6 L of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added, 1160 mL of a 0.1 mol / L sodium hydroxide aqueous solution was added, and the organic layer was separated. The organic layer was washed with 1450 mL of 0.05 mol / L hydrochloric acid, and the organic layer was separated and dehydrated with magnesium sulfate, and then the solvent was removed with an evaporator to obtain 350 g of YM-1.

(Preparation of solution in which prepolymer 1 was dissolved in ethyl acetate)
In a three-necked flask, 6.9 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.0 parts by mass of YM-1 and 24.0 parts by mass of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.07 parts by mass of Neostan U-600 (trade name, manufactured by Nitto Kasei Kogyo Co., Ltd.) was added and stirred at 75 ° C. for 4 hours. Ethyl acetate was added so that the final solid content concentration was 50% by mass, and a solution (prepolymer 1 solution) in which prepolymer 1 was dissolved in ethyl acetate was obtained. The prepolymer 1 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the terminal.

(Preparation of a solution in which prepolymer 2 is dissolved in ethyl acetate)
In a three-necked flask, 24.5 parts by mass of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.5 parts by mass of dimethylolbutanoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) (equivalent to an acid value of 15 mgKOH / g), poly 11.9 parts by mass of caprolactone diol (manufactured by Aldrich, average molecular weight 530), 1.0 part by mass of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.), 105.0 ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) Part by mass, 0.14 part by mass of Neostan U-600 (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name) were added and stirred at 75 ° C. for 4 hours. Ethyl acetate was added so that the final solid content concentration was 50% by mass, and the mixture was filtered to obtain a solution (prepolymer 2 solution) in which prepolymer 2 was dissolved in ethyl acetate. The prepolymer 2 is a polyurethane having a carboxyl group and a urethane bond and having an isocyanate group at the terminal.

(Preparation of aqueous dye polymer dispersion (ULx-8))
In a container, 15.8 parts by mass of the prepolymer 1 solution obtained above, 4.9 parts by mass of the prepolymer 2 solution obtained above, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 10.6 0.3 parts by mass of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a part by weight and neutralizing agent. Furthermore, a mixed liquid of 35.6 parts by mass of pure water and 11.7 parts by mass of a 4% by mass aqueous sodium dodecyl sulfate 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, 2.8 parts by mass of a 10% by mass aqueous solution of UCAT SA102 (trade name, manufactured by San Apro Co., Ltd.) was added to the emulsified liquid, and pure water was added so that the solid concentration was 15% by mass. And prepolymer 1 and prepolymer 2 were reacted for 2 days. Thereafter, coarse particles were removed by filtration to obtain 42 parts by mass of an aqueous dye polymer dispersion (ULx-8). The final solid content concentration of the dye polymer aqueous dispersion (ULx-8) was 15% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-8) was polyurethane / urea, and the average particle size thereof was 184 nm. Moreover, since the insoluble matter remained in any of DMSO, NMP, and THF, the dye polymer was found to be a polymer having a crosslinked structure.

(Example 8)
[Preparation of Yellow Ink 3]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare yellow ink 3.
Dye polymer aqueous dispersion (ULx-8) 3.0 parts by weight Pigment dispersion (Y2) 1.0 part by weight Ultrapure water 5.18 parts by weight Glycerin 0.60 parts by weight Triethylene glycol monobutyl ether 0.12 parts by weight Surfynol 465 (trade name, manufactured by Nissin Chemical Industry) 0.10 parts by mass

[Inkjet printing]
Ink-jet printing was performed in the same manner as in Example 1 except that the yellow ink 3 was used in place of the yellow ink 1 to obtain a colored fabric.

Example 9
Ink-jet printing was performed in the same manner as in Example 4 except that the yellow ink 3 was used in place of the yellow ink 1 to obtain a colored fabric.

(Example 10)
[Preparation of Yellow Ink 4]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare yellow ink 4.
Dye polymer aqueous dispersion (ULx-8) 3.0 parts by mass Pigment dispersion (Y2) 1.0 part by mass Nipol Lx421 (manufactured by Nippon Zeon Co., Ltd.) 0.80 parts by mass Ultrapure water 4.38 parts by mass Glycerin 0.60 parts by mass Triethylene glycol monobutyl ether 0.12 parts by mass Surfynol 465 (manufactured by Nissin Chemical Industry, trade name) 0.10 parts by mass

Nipol Lx421 is a dispersion containing an aqueous dispersion of a carboxyl-modified styrene / butadiene copolymer which is a water-insoluble polymer having no structure derived from a dye. The average particle size of the aqueous dispersion is 100 nm and the solid content is 41% by mass.

[Inkjet printing]
Ink-jet printing was performed in the same manner as in Example 1 except that the yellow ink 4 was used in place of the yellow ink 1 to obtain a colored fabric.

(Example 11)
Ink-jet printing was performed in the same manner as in Example 4 except that the yellow ink 4 was used in place of the yellow ink 1 to obtain a colored fabric.

[Synthesis of (M-1-1)]
With reference to US Pat. No. 6,348,592, 2,2-bis (hydroxymethyl) 2,3-dihydroperimidine as a raw material of (M-1-1) 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. Thereto, 7.3 mL of concentrated hydrochloric acid was added and cooled to 0 to 5 ° C. While maintaining the temperature at 0 to 5 ° C., an 8.5% by mass aqueous solution of sodium nitrite was added dropwise, followed by reaction for 1 hour to obtain a diazonium salt solution. A 3-necked flask was charged with 23 g of 2,2-bis (hydroxymethyl) 2,3-dihydroperimidine and 150 mL of tetrahydrofuran (THF), 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 reaction solution. The reaction solution was filtered and the solid was collected by filtration, washed with pure water until it was free of acetic acid and dried to obtain 40 g of (M-1-1) solid. Analysis of (M-1-1) revealed that LC (Liquid Chromatography) -MS (Mass
Spectrometry) (Nega) 487.2, (Posi) 489.1. FIG. 1 shows the UV (ultraviolet) absorption spectrum of (M-1-1) in a chloroform / methanol = 1/1 solution. “Abs.” In FIG. 1 represents “absorbance”.

(Preparation of Prepolymer 3 in THF)
Into a three-necked flask, 4.4 g of isophorone diisocyanate, 6.5 g of (M-1-1), 25.5 g of THF, 0.03 g of Neostan U-600 (trade name, manufactured by Nitto Kasei Kogyo Co., Ltd.) was added at 65 ° C. Stir for 6 hours. The disappearance of (M-1-1) was confirmed by high performance liquid chromatography. THF was added so that the final solid content concentration was 30% by mass, and a THF solution of prepolymer 3 was obtained.

(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% over 6 minutes to A solution concentration 0% and B solution concentration 100%, and then kept A solution concentration 0% and B solution concentration 100% for 2 minutes. .

(Preparation of Prepolymer 5 in THF)
In a three-necked flask, isophorone diisocyanate 13.1 g, dimethylol butanoic acid 4.0 g, polycaprolactone diol (manufactured by Aldrich, average molecular weight 530) 6.4 g, trimethylol propane 0.5 g, THF 56.0 g, Neostan U-600 ( Nitto Kasei Kogyo Co., Ltd., trade name) 0.7 g was added and stirred at 75 ° C. for 4 hours. THF was added so that the final solid content concentration was 30% by mass to obtain a THF solution of prepolymer 5.

(Preparation of dye polymer aqueous dispersion (ULx-1))
In a container, 16.7 g of a THF solution of the prepolymer 3 obtained as above as a first prepolymer, Takenate D-116N (nonionic dispersion prepolymer, manufactured by Mitsui Chemicals) as a second prepolymer 50 mass A 2.5% ethyl acetate solution, 11.3 g ethyl acetate, and 0.8 g THF were 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 15% by mass. The reaction was held for a day. Thereafter, coarse particles were removed by filtration to obtain 42 g of a black dye polymer aqueous dispersion (ULx-1). The final solid content concentration of the dye polymer aqueous dispersion (ULx-1) was 15% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-1) was polyurethane / urea, and the average particle size (MV) thereof was 95 nm. Moreover, since the insoluble matter remained in any of DMSO, NMP, and THF, the dye polymer was found to be a polymer having a crosslinked structure.

(Preparation of dye polymer aqueous dispersion aqueous dispersion (ULx-2))
In a container, 17.6 g of the THF solution of prepolymer 3 obtained above as the first prepolymer, 3.2 g of 30% by weight THF solution of prepolymer 5 as the second prepolymer, 10.4 g of ethyl acetate, triethylamine 0.1 g 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 15% by mass. The reaction was held for a day. Thereafter, coarse particles were removed by filtration to obtain 40 g of a black dye polymer aqueous dispersion (ULx-2). The final solid content concentration of the dye polymer aqueous dispersion (ULx-2) was 15% by mass. The dye polymer contained in the dye polymer aqueous dispersion (ULx-2) was polyurethane / urea, and the average particle size (MV) thereof was 115 nm. Moreover, since the insoluble matter remained in any of DMSO, NMP, and THF, the dye polymer was found to be a polymer having a crosslinked structure.

(Example 12)
[Preparation of Black Ink 3]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare black ink 3.
Dye polymer aqueous dispersion (ULx-1) 3.5 parts by weight Pigment dispersion (Bk2) 2.5 parts by weight Glycerin 0.4 parts by weight Diethylene glycol 0.3 parts by weight Surfynol 465 (manufactured by Nissin Chemical Industry, trade name) ) 0.1 parts by weight water 3.2 parts by weight

[Inkjet printing]
Temperature of heat treatment using black ink 3 instead of yellow ink 1 as an ink for ink-jet textile printing and using a dried heat press (trade name: desktop automatic flat press machine AF-54TEN type, manufactured by Asahi Textile Machinery Co., Ltd.) Was changed to 180 ° C. instead of 200 ° C., inkjet printing was performed in the same manner as in Example 4 to obtain a colored fabric.

(Example 13)
[Preparation of Black Ink 4]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare black ink 4.
Dye polymer aqueous dispersion (ULx-2) 3.5 parts by weight Pigment dispersion (Bk2) 2.5 parts by weight Glycerin 0.4 parts by weight Diethylene glycol 0.3 parts by weight Surfynol 465 (manufactured by Nissin Chemical Industry, trade name) ) 0.1 parts by weight water 3.2 parts by weight

[Inkjet printing]
Heat treatment temperature using black ink 4 instead of yellow ink 1 as the ink for ink-jet textile printing, and using a heat press after drying (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) Was changed to 180 ° C. instead of 200 ° C., inkjet printing was performed in the same manner as in Example 4 to obtain a colored fabric.

(Example 14)
[Preparation of Black Ink 5]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare black ink 5.
Dye-polymer aqueous dispersion (ULx-2) 6.0 parts by weight Pigment dispersion (Bk2) 0.5 parts by weight Glycerin 0.4 parts by weight Diethylene glycol 0.3 parts by weight Surfynol 465 (manufactured by Nissin Chemical Industry, trade name) ) 0.1 parts by weight water 2.7 parts by weight

[Inkjet printing]
Temperature of heat treatment using black ink 5 instead of yellow ink 1 as an ink for ink jet textile printing and using a heat press after drying (Asahi Textile Machine Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) Was changed to 180 ° C. instead of 200 ° C., inkjet printing was performed in the same manner as in Example 1 to obtain a colored fabric.

(Example 15)
Ink-jet printing was performed in the same manner as in Example 4 except that the black ink 5 was used in place of the yellow ink 1 to obtain a colored fabric.

(Example 16)
[Preparation of Black Ink 6]
The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore size 0.8 μm) to prepare black ink 6.
Dye polymer aqueous dispersion (ULx-2) 3.5 parts by weight Pigment dispersion (Bk2) 2.5 parts by weight WBR-2101 (manufactured by Taisei Fine Chemical Co., Ltd.) 1.0 part by weight Glycerin 0.4 part by weight Diethylene glycol 0.3 Parts by weight Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.1 parts by weight water 2.2 parts by weight

WBR-2101 is a dispersion containing an aqueous dispersion of polyurethane, which is a water-insoluble polymer having no structure derived from a dye, and the content of the aqueous dispersion of polyurethane is 25% by mass. The average particle size (MV) of the body is 41 nm.

[Inkjet printing]
Temperature of heat treatment using black ink 6 instead of yellow ink 1 as an ink for ink-jet textile printing, and using a heat press after drying (product name: desktop flat press machine AF-54TEN type, manufactured by Asahi Textile Machinery Co., Ltd.) Was changed to 180 ° C. instead of 200 ° C., inkjet printing was performed in the same manner as in Example 1 to obtain a colored fabric.

(Example 17)
Ink-jet printing was performed in the same manner as in Example 4 except that the black ink 6 was used in place of the yellow ink 1 to obtain a colored fabric.

The colored cloths obtained in Examples 1 to 17 and Comparative Examples 1 to 3 were evaluated as follows.
In the evaluation of wet friction fastness and washing resistance, cotton cloth was used among the three kinds of cloth.
-Image clarity: The sensory evaluation was performed visually. AA when 3 types of fabric are clear and dark, A when 3 types of fabric are clear, B when 2 types are clear, C when only 1 type is clear, and 4 when there is no clear image D Rated by stage.
-Wet friction fastness: JIS (Japanese Industrial Standard) L-0849 (revised in 2013) Evaluation was made based on the Gakushin type friction test (class 5 method).
The evaluation result of wet friction fastness shows that the larger the value, the better the fastness.
Washing resistance: evaluated according to JIS L-0844 A-2 according to “JIS Handbook 31 Fiber” edited by Japanese Standards Association, published in 2015. Larger numbers indicate better wash resistance.

As the evaluation of the black inks 1 to 6, the following “effect of tightening other colors” was evaluated.

(Effect to tighten other colors)
As a color ink (magenta ink, yellow ink, and cyan ink), a commercially available pigment ink (manufactured by Fujifilm Imaging Colorant, product name Projet TX413) is used, and as the black ink, the above black inks 1 to 6 are used. The image pattern for evaluation shown in FIG. 2 was printed on the cotton fabric, and sensory evaluation was performed visually. A case where the magenta, yellow and cyan color portions appear to be tightened is designated as A, and a portion where the magenta, yellow and cyan portions appear to be blurred is designated as B.
A method for creating an image pattern for evaluation is shown below.
As a black ink, one kind selected from black inks 1 to 6 corresponding to the respective examples or comparative examples and the above-described color inks (magenta ink, yellow ink, and cyan ink) are loaded in an ink cartridge, and an ink jet printer 2 is printed on a cotton fabric (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002) using (Clario PX-045A manufactured by Seiko Epson Corporation). Dry at 20 ° C. for 12 hours. After drying, heat treatment is performed using a heat press (manufactured by Asahi Textile Machinery Co., Ltd., trade name: desktop automatic flat press machine AF-54TEN type) 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. 2, B represents a portion printed in black using black ink, M represents a portion printed in magenta color using magenta ink, and Y represents a portion printed in yellow color using yellow ink. C represents 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, respectively. The interval between the magenta portion and the yellow portion is 3 mm, and the interval between the yellow portion and the cyan portion is 3 mm.

In addition, for all the dye polymers used in the examples, using a melting point measuring machine, the temperature was raised to 200 ° C. at 10 ° C./min, and it was confirmed whether or not it was melted at 200 ° C. The dye polymer melted at 200 ° C.

As is apparent from the above results, it can be seen that the ink for inkjet printing of the example of the present invention gives a colored fabric having excellent image sharpness and friction fastness. In addition, the ink jet textile printing method according to the embodiment of the present invention does not require a pretreatment process, and does not generate waste water and waste materials. Therefore, it is excellent in environmental load and has no problem in workability.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on March 6, 2017 (Japanese Patent Application No. 2017-042071) and a Japanese patent application filed on December 26, 2017 (Japanese Patent Application No. 2017-249902). Incorporated herein by reference.

1 Image pattern for evaluating the effect of tightening other colors for black B Part printed with black C Part printed with cyan Y Part printed with yellow M Part printed with magenta

Claims

An ink containing an aqueous dispersion of a polymer having a structure derived from a dye and a pigment.
The ink according to claim 1, which is for inkjet textile printing.
The pigment 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 according to claim 1, wherein the ink is at least one selected from the group consisting of:
The structure derived from the dye is a structure derived from any dye selected from an azo compound, stilbene, triarylmethane, xanthene, indoaniline, indophenol, nigrosine, anthraquinone, quinophthalone, dicyanostyryl compound, and phthalocyanine. The ink according to any one of claims 1 to 3, further comprising:
The ink according to any one of claims 1 to 4, wherein the polymer having a structure derived from the dye is polyurethane.
The ink according to any one of claims 1 to 5, wherein the polymer having a structure derived from the dye is a polymer having a crosslinked structure.
The ink according to any one of claims 1 to 6, wherein the polymer having a structure derived from the dye melts at 200 ° C.
The ink according to any one of claims 1 to 7, wherein the ink further comprises an aqueous dispersion of a water-insoluble polymer having no structure derived from a dye.
An inkjet printing method comprising a step of directly printing the ink according to any one of claims 1 to 8 on a fabric by an inkjet method.
9. A pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a fabric to obtain a pretreated fabric, and the ink according to any one of claims 1 to 8 by the ink jet method, An ink jet printing method comprising a step of printing on a printed fabric.
Furthermore, the inkjet textile printing method of Claim 9 or 10 including a heat treatment process.
The ink-jet printing method according to claim 11, wherein in the heat treatment step, a polymer having a structure derived from the dye is melted.
An ink cartridge having the ink according to any one of claims 1 to 8.
An ink jet printer having the ink according to any one of claims 1 to 8.
A colored cloth comprising a cloth, a polymer having a structure derived from a dye, and a pigment.