WO2018043416A1

WO2018043416A1 - Printing method, inkjet ink and colored fabric

Info

Publication number: WO2018043416A1
Application number: PCT/JP2017/030768
Authority: WO
Inventors: 藤江　賀彦; 征夫谷; 未奈子原
Original assignee: 富士フイルム株式会社
Priority date: 2016-08-31
Filing date: 2017-08-28
Publication date: 2018-03-08
Also published as: JPWO2018043416A1

Abstract

A printing method and a method for producing a printed material, which have excellent pinning properties, color developability and friction resistance are able to be provided by a printing method and a method for producing a printed material, each of which comprises the steps (A) and (B) described below, an inkjet ink used in these method, an ink cartridge filled with the inkjet ink, a printed material and a colored fabric. In addition, the present invention is able to provide: an inkjet ink which enables the achievement of a printed material that has excellent pinning properties, color developability and friction resistance; an ink cartridge filled with this inkjet ink; a printed material; and a colored fabric. Step (A): a step for applying an inkjet ink to a substrate by an inkjet method, said inkjet ink containing a polymerizable compound, a polymerization initiator, and an aqueous dispersion of a dye polymer (P) having a repeating unit that contains a structure derived from a dye Step (B): a light irradiation step

Description

[Name of invention determined by ISA based on Rule 37.2] Printing method, inkjet ink and colored fabric

The present invention relates to a printing method, a printed material manufacturing method, an inkjet ink, an ink cartridge, a printed material, and a colored cloth.

The ink jet recording method is a method of performing printing by ejecting small droplets of ink from a fine nozzle head, causing them to fly, and adhering to a substrate. This ink jet recording method is characterized in that a high-resolution and high-quality image can be printed at high speed.

As inks used in the ink jet recording method, water-based inks using pigments or dyes as colorants are widely used. Water-based inks are excellent in terms of safety and environmental problems, but have a problem that bleeding tends to occur when printing on high-quality paper or plain paper. Further, there may be a problem that the printed ink cannot be fixed on a recording medium that does not absorb ink, for example, a polymer resin film, earthenware, or a glass substrate. In order to solve such a problem, an aqueous photocurable ink containing a colorant, a polymerizable compound, and a polymerization initiator has been proposed.

For example, Patent Document 1 describes a water-based ink composition containing a color material, a polymerizable compound, and a photopolymerization initiator. Patent Document 2 describes an ink composition for textile printing containing a dye, a polymerizable compound, and a photopolymerization initiator.

Patent Document 3 describes an ink-jet ink containing a polymer having a specific structure in which a specific dye is linked to a polymer skeleton.
Patent Document 4 describes an ink-jet ink containing polyurethane having a colorant structure.

Japanese Unexamined Patent Publication No. 2016-089123 Japanese Unexamined Patent Publication No. 2016-060815 Japan Special Table 2004-534106 Japan Special Table 2002-509957

However, inks using conventionally known pigments have a problem that the color developability of the ink and the friction resistance of the obtained image are insufficient. In addition, in order to make the photocurable ink into a semi-cured state, an operation such as so-called pinning, which is irradiated with light such as ultraviolet rays, may be performed, but the affinity between the pigment and the polymerizable compound is low, and the pigment is used during photocuring. The problem of the occurrence of non-uniform aggregation (poor pinning property) has not been sufficiently solved. On the other hand, in the ink using a conventionally known dye, there is a problem that the pinning property is inferior due to the ability of the dye to inhibit polymerization, and the dyeing property is deteriorated by the pinning, resulting in inferior abrasion resistance of the obtained image.

SUMMARY OF THE INVENTION An object of the present invention is to provide a printing method and a printed matter manufacturing method that have good color developability and friction resistance and excellent pinning properties. Another object of the present invention is to provide an inkjet ink, an ink cartridge filled with the inkjet ink, a printed matter, and a colored cloth that can provide a printed matter having good color development and friction resistance and excellent pinning properties. That is.

In order to solve the above-mentioned problems, the present inventors have conducted intensive research and used an aqueous dispersion of a dye polymer having a repeating unit containing a structure derived from a dye, a polymerizable compound, and an ink containing a polymerization initiator, It has been found that a printed matter excellent in pinning property, color developability and friction resistance can be obtained by a method of printing on a substrate by an ink jet method.
In addition, when the substrate is a fabric, it has been found that fastness such as washing resistance, sweat resistance, friction resistance, and dry cleaning resistance of the obtained image is remarkably improved.
Although details are unknown as a mechanism by which the above problem can be solved by the above method, the present inventors presume as follows.
When a dye polymer, a polymerizable compound, and a polymerization initiator are used in combination, a pinning treatment or a heat treatment is performed, so that the polymer formed by the polymerizable compound on the surface of the substrate and the dye polymer are intertwined with each other, and the tertiary It is thought that an original dense polymer film is formed and the friction resistance of the image is improved. In addition, the dye polymer has a structure derived from a dye, has excellent color developability, and since it is a polymer, it has excellent compatibility with a polymerizable compound and has good pinning properties.
Specifically, the object of the present invention has been achieved by the following means.

<1>
A printing method comprising the following steps (A) and (B).
Step (A): A step of applying an ink jet ink containing an aqueous dispersion of a dye polymer (P) having a repeating unit containing a structure derived from a dye, a polymerizable compound, and a polymerization initiator to the substrate by an ink jet method. (B): Light irradiation step <2>
Furthermore, the printing method as described in <1> including a process (C) heat processing process.
<3>
The printing method according to <1> or <2>, wherein the substrate is a fabric.
<4>
The printing method according to <2>, wherein the temperature of the heat treatment in the step (C) is 50 ° C. or higher and lower than 250 ° C.
<5>
Any one of <1> to <4>, wherein the dye polymer (P) in the aqueous dispersion is a particulate dye polymer, and the average particle diameter of the particulate dye polymer is 50 to 500 nm. The printing method described.
<6>
The printing method according to any one of <1> to <5>, wherein the dye polymer (P) has a weight average molecular weight of 3,000 to 200,000.
<7>
The printing method according to any one of <1> to <6>, wherein the content of the polymerizable compound is 1 to 30% by mass with respect to the total amount of the inkjet ink.
<8>
The manufacturing method of printed matter including the following process (A) and (B).
Step (A): A step of applying an inkjet ink containing an aqueous dispersion of a dye polymer (P) having a repeating unit containing a structure derived from a dye, a polymerizable compound, and a polymerization initiator to the fabric by an inkjet method. B): Light irradiation step <9>
Furthermore, the manufacturing method of the printed matter as described in <8> including a process (C) heat processing process.
<10>
An ink-jet ink comprising an aqueous dispersion of a dye polymer (P) having a repeating unit containing a structure derived from a dye, a polymerizable compound, and a polymerization initiator.
<11>
The inkjet ink according to <10>, which is for textile printing.
<12>
An ink cartridge filled with the inkjet ink according to <10> or <11>.
<13>
A printed matter having an image containing a dye polymer having a repeating unit containing a structure derived from a dye and a polymer different from the dye polymer on at least a part of the surface of the substrate.
<14>
A colored cloth having an image containing a dye polymer having a repeating unit containing a structure derived from a dye and a polymer different from the dye polymer on at least a part of the surface of the cloth.

According to the present invention, it is possible to provide a printing method and a printed matter manufacturing method that are excellent in pinning property, coloring property, and friction resistance. Moreover, according to this invention, the inkjet ink which can provide the printed matter excellent in pinning property, coloring property, and abrasion resistance, the ink cartridge filled with the inkjet ink, printed matter, and a colored cloth can be provided. .

Hereinafter, the present invention will be described in detail.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents at least one of acrylate and methacrylate, “(meth) acryl” represents at least one of acryl and methacryl, and “(meth) acryloyl” represents at least acryloyl and methacryloyl. Represents a kind.

[Printing method]
The printing method of the present invention is a printing method including the following steps (A) and (B).

Step (A): A step of applying an ink jet ink containing an aqueous dispersion of a dye polymer (P) having a repeating unit containing a structure derived from a dye, a polymerizable compound, and a polymerization initiator to the substrate by an ink jet method. (B): Light irradiation process

<Process (A)>
Step (A) is a step of applying an inkjet ink containing an aqueous dispersion of the dye polymer (P), a polymerizable compound, and a polymerization initiator to the substrate by an inkjet method.

<Process (B)>
Step (B) is a light irradiation step. More specifically, the step (B) is formed by inkjet ink by irradiating light (typically actinic rays) to the substrate to which the inkjet ink is applied. This is a step of curing the image. This is because the polymerization initiator contained in the inkjet ink is decomposed by irradiation with actinic rays to generate polymerization initiation species such as radicals, and the polymerization reaction of the polymerizable compound occurs and accelerates in the function of the polymerization initiation species. It is to be done.

In a printing method in which a polymerization reaction of a polymerizable compound proceeds to cure an image formed with an inkjet ink, image curing by light irradiation is preferable. Since image curing by light irradiation proceeds at high speed, the drying (curing) system can be greatly simplified. In the printing method of the present invention, the polymerization reaction may be completed in step (B), or a part of the polymerization reaction may be performed in step (B).

In the step (B) of the printing method of the present invention, a preferable first aspect is to proceed the polymerization reaction of the polymerizable compound to completely cure the image formed by the inkjet ink.
Further, as the step (B), it is preferable that a part of the polymerization reaction is performed in the step (B), and an uncured portion of the image formed by the ink jet ink is cured by heat treatment in the step (C) described later. It is mentioned as 2nd aspect.
From the viewpoint of facilitating complete curing by melting the dye polymer by heat treatment, the second embodiment is more preferable.

~ Pre-curing process ~
In a preferred first embodiment of the step (B), it is preferable to provide a pre-curing step for pre-curing the inkjet ink applied on the substrate.
For example, in the case of forming an image using two or more colors of ink-jet ink, the pre-curing step is performed after applying the first ink-jet ink on the substrate and before applying the second ink-jet ink. The inkjet ink is preferably pre-cured by light irradiation (also referred to as pinning exposure). Pinning exposure is an exposure method in which ink jet ink applied to a substrate is partially cured with a light amount that is insufficient for complete curing.
When an image of two or more colors is formed, the ink on the base material is thickened by performing pinning exposure for each color, so that occurrence of so-called color bleeding between colors can be suppressed.

The exposure amount of pinning exposure for pre-curing is preferably less than half of the exposure amount for main curing in the curing step described later, and more preferably less than one-quarter.

The light source used for pre-curing is not particularly limited as long as it is a light source that emits light having a wavelength that promotes polymerization and curing of the ink jet ink. be able to.

As the time from the landing of the ink-jet ink to the actinic ray irradiation and the actinic ray irradiation time, preferred times in the curing step described later can be applied.

~ Curing process ~
In said 1st aspect, the image formed with the inkjet ink provided on the base material is fully hardened in a process (B).

The actinic rays are preferably α rays, γ rays, electron beams, X rays, ultraviolet rays (UV), visible light or infrared light. The peak wavelength of the actinic ray depends on the absorption characteristics of the sensitizer, but is preferably 200 to 600 nm, more preferably 300 to 450 nm, still more preferably 320 to 420 nm, and the actinic ray is an ultraviolet ray having a peak wavelength of 340 to 400 nm. It is particularly preferred that

As the illumination intensity on the exposed surface of the ink-jet ink used in the present invention ^is preferably 10mW / cm 2 ~ 4,000mW / cm 2, more preferably ^{20mW / cm 2 ~ 2,500mW / cm} 2.

Mercury lamps, gas or solid lasers are mainly used as actinic light sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing ultraviolet light curable inkjet inks. However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally.
In addition, a light emitting diode (LED) and a laser diode (LD) can be used as the active light source. These are small, have a long service life, have high efficiency, and are low in cost, and are expected as light sources for photo-curable ink jets. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit active light centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic ray source particularly preferred in the present invention is a UV-LED, and particularly preferably a UV-LED having a peak wavelength at 340 to 400 nm.
The maximum illumination intensity on the LED substrate ^is preferably 10mW / cm 2 ~ 2000mW / cm 2, more preferably 20mW / cm 2 ~ 1000mW / cm 2, 50mW / cm 2 ~ 800mW / Cm ² is particularly preferred.

The inkjet ink used in the present invention is suitably irradiated with such actinic rays preferably for 0.01 seconds to 120 seconds, more preferably for 0.1 seconds to 90 seconds.
An actinic ray irradiation condition and a basic irradiation method are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the ink jet ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method. Irradiation with actinic rays is performed for a certain time (preferably 0.01 seconds to 0.5 seconds, more preferably 0.01 seconds to 0.3 seconds, still more preferably 0.01 seconds to 0. 15 seconds). Thus, by controlling the time from the landing of the ink jet ink to the irradiation in an extremely short time, it is possible to prevent the ink jet ink that has landed on the recording medium from spreading before being cured. Moreover, since it can expose before an inkjet ink osmose | permeates to the deep part which a light source does not reach also with respect to a porous base material, since the residue of an unreacted monomer can be suppressed, it is preferable.
Further, curing may be completed by another light source that is not driven. As an irradiation method, for example, as described in the pamphlet of International Publication No. 99/54415, a method using an optical fiber or a collimated light source is applied to a mirror surface provided on the side of the head unit, and the recording unit is irradiated with UV. Methods can also be applied.

It is also preferable that the atmosphere around the surface of the recording medium is an oxygen-poor atmosphere when irradiated with actinic rays. By suppressing the oxygen concentration in the curing atmosphere, the energy of actinic rays necessary for curing can be reduced.

In the second aspect of the step (B), only a part of the polymerization reaction of the polymerizable compound is performed in the step (B), and the image formed by the inkjet ink is partially cured. Curing conditions (exposure amount, time until exposure after ink jet ink landing, exposure time) and the light source used for curing may be the curing conditions and light source described in the pre-curing step in the first aspect. preferable. That is, a preferred second embodiment is one in which the inkjet ink applied to the substrate in the step (B) is temporarily hardened by pinning exposure, and the curing of the inkjet ink pinned in the step (C) is completed.

Further, after the step (B), before the following step (C), a substrate drying step may be provided if necessary. The drying temperature is preferably 10 to 100 ° C, more preferably 15 to 80 ° C, and particularly preferably 20 to 60 ° C. The drying time is preferably 1 to 24 hours, more preferably 2 to 18 hours, and particularly preferably 2 to 12 hours. It is preferable to provide a drying step because the sharpness of the printed image is excellent.

<Process (C)>
The printing method of the present invention preferably further includes a heat treatment step as step (C). In particular, by performing a heat treatment step after printing an image on the substrate, the particulate dye polymer can be melted (or softened), and the adhesion to the substrate can be improved (that is, by heat treatment, Can be melt dyed).
The temperature of the heat treatment in the step (C) is preferably 50 ° C. or higher and lower than 250 ° C., more preferably 60 to 200 ° C., and further preferably 80 to 180 ° C. By setting it as the said range, the effect of this invention can fully be exhibited. The heat treatment time is preferably 15 to 360 seconds, more preferably 30 to 180 seconds. By setting it within this range, the effect of the present invention can be sufficiently and stably exhibited. If the heat treatment time is too long, the fabric is greatly damaged and the texture of the fabric is deteriorated. If the heat treatment time is too short, the polymerization reaction is not completed sufficiently and the effects of the present invention cannot be exhibited.
Since the heat treatment step is preferably performed at the above temperature, the dye polymer is preferably melted at less than 250 ° C, more preferably melted at 200 ° C or less, and further preferably melted at 180 ° C or less.
Whether the dye polymer melts at a specific temperature can be confirmed by raising the temperature of the dye polymer to a specific temperature at 10 ° C./min with a melting point measuring instrument and visually checking the state of the dye polymer.
In the second aspect of the step (B), it is preferable to accelerate the polymerization reaction of the unreacted polymerizable compound in this heat treatment step and to cure the image. Therefore, the polymerizable compound is preferably a photopolymerizable compound and a thermopolymerizable compound at the same time.

<Post-processing>
When the substrate is a fabric, the fabric (colored fabric) colored by the printing method of the present invention (which is also a textile printing method in this case) is excellent in the flexibility and fastness of the texture. Further, by performing padding treatment on the entire surface of the post-treatment agent, it is possible to obtain a colored cloth having further improved texture flexibility and fastness (particularly 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 emulsion or 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.

Hereinafter, each component used in the present invention will be described in detail.

The ink-jet ink used in the printing method of the present invention contains a polymerizable compound and a polymerization initiator for the purpose of improving the fixability of the image on the substrate and the friction resistance.
In the printing method of the present invention, the polymerizable compound and the polymerization initiator may be photopolymerizable or heat polymerizable, but image curing proceeds by light irradiation in the step (B). The photopolymerizable compound and the photopolymerization initiator are preferred.
It is also preferable that the photopolymerizable compound is a thermopolymerizable compound. By having thermal polymerizability, the polymerization reaction can be advanced also in the step (C).

<Polymerizable compound>
The ink-jet ink used in the present invention preferably contains at least one water-soluble photopolymerizable compound having an ethylenically unsaturated bond as the polymerizable compound.
The polymerizable compound may be any water-soluble compound having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule, and has a chemical form such as a monomer, oligomer, or polymer. included. Only one type of polymerizable compound may be used, or two or more types may be used in combination at an arbitrary ratio in order to improve the desired properties. It is preferable to use two or more kinds in combination for controlling performance such as reactivity and physical properties. Further, from the viewpoint of ink ejection stability, it is preferable to use a compound that has good solubility in water and hardly precipitates in the aqueous ink composition.

The water-soluble polymerizable compound means a compound that dissolves in 2% by mass or more in distilled water at 25 ° C., but preferably dissolves in an amount of 15% by mass or more, and particularly those that are uniformly mixed with water at an arbitrary ratio. preferable.

Examples of polymerizable compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, and their ester derivatives and their salts, acrylamide and methacrylamide and their Derivatives, anhydrides having ethylenically unsaturated groups, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethanes, vinyl ethers, allyl ethers, etc., acrylic acid and methacrylic acid And at least one selected from ester derivatives and salts thereof, acrylamide and methacrylamide, and derivatives thereof, and monoesters of acrylic acid or methacrylic acid (hereinafter referred to as “monoacrylate”) ), An ester of acrylic acid or methacrylic acid and a polyol compound (hereinafter sometimes referred to as “polyfunctional acrylate monomer” or “polyfunctional acrylate oligomer”), or at least one of acrylamide or methacrylamide and derivatives thereof More preferably it is a seed.

The polymerizable compound preferably has at least one of a poly (ethyleneoxy) chain, a poly (propyleneoxy) chain, an ionic group (for example, a carboxyl group, a sulfo group, etc.) and a hydroxyl group from the viewpoint of imparting water solubility. .
When the polymerizable compound has a poly (ethyleneoxy) chain or a poly (propyleneoxy) chain, the number of ethyleneoxy units and units of propyleneoxy units is preferably in the range of 1 to 10, more preferably 1 It is in the range of ~ 5. When the number of units is 10 or less, the hardness of the coating when cured and the adhesion to the substrate are improved.

Among the polymerizable compounds, particularly preferred specific examples of the monoacrylate, polyfunctional acrylate monomer, polyfunctional acrylate oligomer, and (meth) acrylamide derivative include, for example, compounds having the structures shown below, but are not limited thereto. Is not to be done.

In addition to the above exemplified compounds, compounds having an ionic group such as methacrylic acid and potassium salt of 3-sulfopropyl acrylate are also preferably used.
In this invention, a polymeric compound may be used individually by 1 type or in combination of 2 or more types.

In the present invention, in order to further improve the sensitivity, bleeding, and adhesion to the substrate, as the polymerizable compound, at least one monoacrylate and a polyfunctional acrylate monomer having a molecular weight of 400 or more, preferably 500 or more, It is preferable to use a polyfunctional acrylate oligomer in combination. In particular, in an inkjet ink used for recording on a flexible substrate such as a resin film, a combination of a monoacrylate selected from the above compound group and a polyfunctional acrylate monomer or polyfunctional acrylate oligomer is acceptable for the film. This is preferable because the film strength can be increased while imparting flexibility to improve adhesion.
In addition, the aspect in which at least three kinds of polymerizable compounds of monofunctional, bifunctional, and trifunctional or higher polyfunctional monomers are used in combination improves sensitivity, bleeding, and adhesion to the substrate while maintaining safety. This is preferable from the viewpoint of further improvement.

In the present invention, from the viewpoints of transparency (colorless and transparent), flexibility, flexibility, surface hardness, and adhesion, it is also preferable that the polymerizable compound is in the form of a polymer. The polymerizable compound in the form of a polymer (hereinafter referred to as “polymerizable polymer”) is a polymer containing a polymerizable functional group in the main chain or side chain of a polymer.
The polymerizable group introduced into the polymer polymer serves as a bridge between the polymers, and improves transparency, flexibility, flexibility, surface hardness, adhesion, and the like. In this respect, examples of the polymerizable polymer are preferably poly (glycidyl (meth) acrylate modified (meth) acrylic acid-co- (meth) acrylate), poly (glycidyl (meth) acrylate modified (meth) acrylic acid) co-meth (acrylate) -co-styrene), poly (styrene-co-4-hydroxybutyl acrylate glycidyl ether-modified acrylic acid), and the like.

As the polymerizable polymer in the present invention, the amount of the polymerizable functional group introduced is preferably 0.01 mmol / g or more and 10 mmol / g or less in order to sufficiently exhibit the effects of the present invention, and 0.1 mmol / g. It is more preferably 5 mmol / g or less and more preferably 0.5 mmol / g or more and 3 mmol or less.

The polymerizable polymer in the present invention is preferably in the form of water-soluble or aqueous latex from the viewpoint of ink jetting properties.

When the polymerizable polymer is water-soluble, the water solubility at 25 ° C. is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. When the polymerizable polymer is water-soluble, the average molecular weight in terms of polystyrene (or polymethacrylic acid) in gel permeation chromatography (GPC) measurement is preferably 3,000 or more and 2,000,000 or less, and 5,000. It is more preferably 1,500,000 or less, and particularly preferably 10,000 or more, 1,000,000 or less. The details of the GPC conditions are the same as those for the dye polymer (P) described later.

When the polymerizable polymer is an aqueous latex, the average particle size is preferably 1 to 500 nm, more preferably 10 to 300 nm, and particularly preferably 30 to 200 nm. When the polymerizable polymer is an aqueous latex, the average molecular weight in terms of polystyrene (or polymethacrylic acid) in GPC measurement is preferably 3,000 or more and 2,000,000 or less, and 5,000 or more and 1,500,000. The following is more preferable, and 10,000 to 1,000,000 is particularly preferable.

Furthermore, a mode in which a polymerizable compound of a monofunctional, bifunctional, or trifunctional or higher polyfunctional monomer is used in combination is also preferable from the viewpoint that sensitivity, bleeding, and adhesion to a substrate can be further improved.

Preferable specific examples of the polymerizable polymer include, but are not limited to, compounds having the following structures. Me represents a methyl group.

The polymerizable compound is preferably a bifunctional methacrylate monomer, a trifunctional or higher functional methacrylate monomer, a polymerizable polymer, or a combination thereof, more preferably a polymerizable polymer, and poly (styrene-co-4- Hydroxybutyl acrylate glycidyl ether modified acrylic acid), poly (ethylene glycol) -poly (styrene-co-4-hydroxybutyl acrylate glycidyl ether modified acrylic acid), poly (styrene-co-glycidyl (meth) acrylate modified acrylic acid), Or, poly (benzyl methacrylate-co-glycidyl methacrylate-modified methacrylic acid) is particularly preferable.

<Polymerization initiator>
The ink-jet ink used in the present invention contains a polymerization initiator. The polymerization initiator is not particularly limited as long as it has a good polymerization initiating ability, and can be selected from known polymerization initiators. Among the polymerization initiators, a water-soluble photopolymerization initiator is preferable. The degree of “water solubility” is preferably 0.5% by mass or more, preferably 1% by mass or more, and particularly preferably 3% by mass or more in distilled water at 25 ° C.

Among the polymerization initiators, polymerization initiators selected from the group consisting of α-aminoketone compounds and acylphosphine oxide compounds are preferred.

As the α-aminoketone compound, a compound having a structure represented by the following general formula (5) is preferably used.

In the general formula (5), Ar ^1D represents a phenyl group substituted with —SR ⁵¹ or —N (R ⁵² ) (R ⁵³ ), and R ⁵¹ represents a hydrogen atom or an unsubstituted alkyl group. To express. R ⁵² and R ⁵³ are each independently a hydrogen atom, an unsubstituted alkyl group having 1 to 12 carbon atoms, an alkoxy substituted alkyl group having 2 to 4 carbon atoms, or an unsubstituted carbon group. Represents an alkenyl group of formula 3-5. R ⁵² and R ⁵³ may combine with each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group contains —O— or —N (R ⁵⁴ ) — in the alkylene chain. There may be. R ⁵⁴ represents an unsubstituted alkyl group having 1 to 4 carbon atoms.

R ^1D and R ^2D each independently represent an unsubstituted alkyl group having 1 to 8 carbon atoms. R ^1D and R ^2D may combine with each other to form an alkylene group having 2 to 9 carbon atoms. R ^3D and R ^4D each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 12 carbon atoms, an alkoxy substituted alkyl group having 2 to 4 carbon atoms, or an unsubstituted carbon number. Represents 3 to 5 alkenyl groups. Here, R ^3D and R ^4D may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group has —O— or —N (R ⁵⁴ ) — in the alkylene chain. It may be included. R ⁵⁴ represents an unsubstituted alkyl group having 1 to 4 carbon atoms.

Examples of the compound contained in the α-aminoketone compound include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2-morpholino. Propan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like. Also, commercially available products such as Irgacure series manufactured by BASF, such as Irgacure 907, Irgacure 369, and Irgacure 379, are also compounds included in α-aminoketone compounds.

As the acylphosphine oxide compound, a compound represented by the following general formula (6) or general formula (7) is preferable.

In the general formula (6), R ^5D and R ^6D each independently represent an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, or a heterocyclic group, and R ^7D represents an aliphatic group. Represents an aromatic group or a heterocyclic group.

Examples of the aliphatic group represented by R ^5D , R ^6D , or R ^7D include an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted alkenyl group, a substituted alkenyl group, an unsubstituted alkynyl group, a substituted alkynyl group, and an unsubstituted group. An aralkyl group or a substituted aralkyl group is exemplified, among which an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted alkenyl group, a substituted alkenyl group, an unsubstituted aralkyl group, or a substituted aralkyl group is preferable, an unsubstituted alkyl group, a substituted aralkyl group, etc. Alkyl groups are particularly preferred. The aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

Examples of the substituted or unsubstituted alkyl group include linear, branched, and cyclic alkyl groups, and the number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 20. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, cyclohexyl, cyclopentyl, neopentyl, An isopropyl group, an isobutyl group, etc. are mentioned.

Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (for example, methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, carbon number 30 The following alkoxy groups (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio groups having 30 or less carbon atoms (for example, methylthio group, ethylthio group, methylthioethylthioethyl group) ), An aryloxy group having 30 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, alkyl group having 30 or less carbon atoms, alkoxycarbonyloxy group, aryl An oxycarbonyloxy group, an acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl group (for example, Carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group) Group), aryl having 30 or less carbon atoms (Eg, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (eg, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino) Group), substituted ureido group, substituted phosphono group, heterocyclic group and the like. Here, the carboxyl group, the sulfo group, the hydroxy group, and the phosphono group may be in a salt state.

Examples of the substituted or unsubstituted alkenyl group include linear, branched, and cyclic alkenyl groups. The number of carbon atoms in the alkenyl group is preferably 2 to 30, and more preferably 2 to 20. Examples of the substituent of the substituted alkenyl group include the same substituents as those of the substituted alkyl group.

Examples of the substituted or unsubstituted alkynyl group include linear, branched, and cyclic alkynyl groups, and the number of carbon atoms of the alkynyl group is preferably 2 to 30, and more preferably 2 to 20. Examples of the substituent for the substituted alkynyl group include the same substituents as those for the substituted alkyl group.

Examples of the substituted or unsubstituted aralkyl group include linear, branched, and cyclic aralkyl groups, and the number of carbon atoms in the aralkyl group is preferably 7 to 35, and more preferably 7 to 25. Examples of the substituent for the substituted aralkyl group include the same substituents as those for the substituted alkyl group.

Examples of the aromatic group represented by R ^5D , R ^6D , or R ^7D include an unsubstituted aryl group and a substituted aryl group. The number of carbon atoms in the substituted or unsubstituted aryl group is preferably 6 to 30, and more preferably 6 to 20. Examples of the aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. Examples of the substituent for the substituted aryl group include the same substituents as those for the substituted alkyl group, in addition to the alkyl group having 1 to 12 carbon atoms.

The aliphatic oxy group represented by R ^5D or R ^6D is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, a phenoxy group. An ethoxy group etc. are mentioned. However, it is not limited to these.

The aromatic oxy group represented by R ^5D or R ^6D is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy group, methylphenyloxy group, chlorophenyloxy group, methoxy Examples thereof include a phenyloxy group and an octyloxyphenyloxy group. However, it is not limited to these.

The heterocyclic group represented by R ^5D , R ^6D , or R ^7D is preferably a heterocyclic group containing a nitrogen atom, an oxygen atom or a sulfur atom, and is a substituted or unsubstituted heterocyclic group such as pyridyl. Group, furyl group, thienyl group, imidazolyl group, pyrrolyl group and the like.

In the general formula (7), R ^8D and R ^10D each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ^9D represents Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic group. Examples of the substituent in the case of having a substituent include the same substituents as those in the general formula (6).

As the substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxy group and substituted or unsubstituted aryloxy group in the general formula (7), , Which has the same meaning as in the general formula (6).

Of the above, for example, [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide] is available under the trade name Irgacure TPO (manufactured by BASF) and [bis (2,4,6-trimethyl). Benzoyl) -phenylphosphine oxide] is available under the trade name Irgacure 819 (BASF).

Furthermore, water-soluble acylphosphine oxide compounds are preferably used as the polymerization initiator. This acylphosphine oxide compound is preferably dissolved in distilled water at 25 ° C. in an amount of 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 3% by mass or more.

Specific examples of water-soluble acylphosphine oxide compounds include compounds described in JP-A No. 2005-307199 (for example, Exemplified Compounds 5, 6, and 7). Preferred specific examples of water-soluble acylphosphine oxide compounds (Exemplary compounds 1-1 to 1-3) are listed below. However, it is not limited to these.

As the polymerization initiator, acylphosphine oxide compounds are preferable.
In addition to the above polymerization initiator, other polymerizable initiators may be used as long as the effects of the present invention are not impaired. Further, it can be used in combination with an acylphosphine oxide compound. In this case, it is preferable to use a water-soluble polymerization initiator. The “water solubility” is the same as described above.

Examples of the other polymerization initiator include camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, such as α-hydroxycycloalkyl phenyl ketones or 2-hydroxy-2-methyl-1-phenyl-propanone, Alkoxyacetophenones, α-hydroxy- or 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers, and benzyl ketals such as benzyl dimethyl ketal, phenyl glyoxalate and its derivatives, dimeric phenyl glyoxalate, Peresters such as benzophenone tetracarboxylic acid peresters (for example those described in EP 1 126541), halomethyltriazines such as 2- [2- (4-methoxy-phen Nyl) -vinyl] -4,6-bis-trichloromethyl [1,3,5] triazine, 2- (4-methoxy-phenyl) -4,6-bis-trichloromethyl [1,3,5] triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trichloromethyl [1,3,5] triazine, 2-methyl-4,6-bis-trichloromethyl [1,3,5] triazine, Hexaarylbisimidazole / co-initiator systems such as ortho-chlorohexaphenyl-bisimidazole in combination with 2-mercaptobenzothiazole; ferrocenium compounds or titanocenes such as dicyclopentadienyl-bis (2, 6-difluoro-3-pyrrolo-phenyl) titanium; for example described in GB 2,339,571 It is also possible to use a mixture of O- acyl oxime ester compound. A boric acid compound can also be used as a co-initiator.

<Dye polymer (P)>
The dye polymer (P) used in the present invention is a pigment multimer containing a structure derived from an arbitrary dye as a repeating unit.
The structure derived from a dye is a group (dye residue) formed by removing one or more arbitrary hydrogen atoms from a compound used as a dye.
The structure derived from the dye is a structure derived from an organic pigment as classified by the color index. For example, azo (monoazo, disazo, trisazo, polyazo), stilbene, carotenoid, diarylmethane, triarylmethane, Examples include xanthene, acridine, quinoline, methine, aniline, indamine, indophenol, azine, oxazine, thiazine, anthraquinone, indigo, quinophthalone, and phthalocyanine. From the viewpoint of coloring power, azo, stilbene, diarylmethane, triarylmethane, xanthene, indophenol, quinophthalone, phthalocyanine, and the like can be preferably used.
As a structure derived from a dye, a structure derived from a dye as categorized by the above color index, or a structure in which an arbitrary substituent is substituted within the range in which the effect of the present invention is obtained, or a structure thereof Examples include a structure in which an arbitrary substituent is removed from the structure within the range where the effects of the present invention are achieved.
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 (P), a polymer containing a structure derived from a dye in the side chain is particularly preferably used. Although it does not specifically limit as a polymer which comprises the principal chain in the polymer containing the structure derived from a dye in a side chain, An acrylic polymer, a urethane polymer, or a styrene polymer is used preferably.
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. “(Meth) acrylic acid” represents at least one of acrylic acid and methacrylic acid, and “(meth) acrylic ester” represents at least one of acrylic acid ester and methacrylic acid ester.
The urethane polymer (also referred to as “polyurethane”) in the present invention is a polymer having a urethane bond, and is formed by a reaction between a polyol compound having two or more hydroxyl groups and a polyisocyanate compound having two or more isocyanate groups. The

In the dye polymer (P), a method of introducing a repeating unit containing a structure derived from a dye is arbitrary, and a polymer may be obtained by polymerizing or copolymerizing a polymerizable dye monomer. After the formation, a structure derived from a dye may be introduced by a polymer reaction or the like.
The dye polymer (P) is preferably a dye polymer including a repeating unit represented by the following general formula (1) as a repeating unit including a structure derived from a dye.

In General Formula (1), X ¹ represents a linking group, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye.

In general formula (1), X ¹ represents a linking group. X ¹ is preferably a linking group formed by polymerization, and preferably a portion corresponding to the main chain formed by the polymerization reaction. That is, X ¹ is preferably a partial structure of the polymer main chain. Examples of X ¹ include a linking group formed by polymerizing a substituted or unsubstituted unsaturated ethylene group, a linking group formed by ring-opening polymerization of a cyclic ether, and the like. Preferably, an unsaturated ethylene group is polymerized. A linking group formed as described above. Specific examples include, but are not limited to, the following linking groups. In the following (X-1) to (X-15), it is linked to L ¹ at the site indicated by *.

The repeating unit represented by the general formula (1) is preferably a repeating unit represented by any one of the following general formulas (1-1) to (1-7). It is more preferable that it is the repeating unit represented by these.

In the general formulas (1-1) to (1-7), R _X1 to R _X21 each represents a hydrogen atom or a substituent, L ¹ represents a single bond or a divalent linking group, and D ¹ represents an arbitrary ^one from a dye. Represents a dye residue from which one hydrogen atom is removed.
When R _X1 to R _X21 represent a substituent, the substituent is preferably an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, or a group formed by a combination thereof, more preferably an alkyl group. More preferably, it is a methyl group.
R _X1 , R _X6 , R _X13 , R _X16 , and R _X19 preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group, a carboxymethyl group, a hydroxymethyl group, or a methyloxymethyl group, and a hydrogen atom or methyl More preferably it represents a group.
R _X2 , R _X3 , R _X4 , R _X5 , R _X7 , R _X8 , R _X9 , R _X10 , R _X11 , R _X12 , R _X14 , R _X15 , R _X17 , R _X18 , R _X20 , and R _X21 It preferably represents an atom or a carboxyl group, and more preferably represents a hydrogen atom.

In general formulas (1) and (1-1) to (1-7), L ¹ represents a single bond or a divalent linking group. The divalent linking group in the case where L ¹ represents a divalent linking group is not particularly limited as long as the effects of the present invention can be obtained, but it is a substituted or unsubstituted straight chain having 1 to 30 carbon atoms, Branched or cyclic alkylene group (for example, methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted arylene group having 6 to 30 carbon atoms (for example, phenylene group, naphthalene group, etc.), substituted Or an unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—, —NR— (R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), —C. (═O) —, —SO—, —SO ₂ —, and a linking group formed by linking two or more of these are preferably used. In particular, a linking group represented by any of the following general formulas (2) to (7) is preferably used.
When L ¹ represents a divalent linking group, the divalent linking group may have a substituent (for example, an alkyl group, an aryl group, a hydroxyl group, an acyloxy group, etc.).

In general formulas (2) to (7), one of * 1 and * 2 is X ¹ in general formula (1) or carbon atom of the polymer main chain in general formulas (1-1) to (1-7) Alternatively, it represents a position bonded to a nitrogen atom, and the other represents a position bonded to D ¹ in the general formulas (1) and (1-1) to (1-7). (1) ^{X 1} or the general formula in (1-1) to represent the position at which the group bonds to a carbon atom or nitrogen atom of the polymer backbone in (1-7), * 2, the general formula (1), (1- It is preferable to represent the position bonded to D ¹ in 1) to (1-7).
In general formula (2), R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (3), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (4), R ² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ³ represents a substituent. k represents an integer of 0 to 4. When k is 2 or more, R ³ may be the same or different.
In General Formula (5), R ₅₁ and R ₅₂ each independently represent a hydrogen atom or a substituent. t represents an integer of 1 to 10. The t R ₅₁ and R ₅₂ may be the same or different.
In General Formula (6), R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a substituent. u and v each independently represents an integer of 1 to 10. u R ⁶¹ and R ⁶² may be the same or different. The v R ⁶³ and R ⁶⁴ may be the same or different.
In general formula (7), R ⁷¹ , R ⁷² and R ⁷³ each independently represent a hydrogen atom or a substituent. w represents an integer of 1 to 10. Each of w R ⁷¹ and R ⁷² may be the same or different.

Examples of the alkyl group, aryl group, or heterocyclic group in the case where R ² in the general formula (3) represents an alkyl group, an aryl group, or a heterocyclic group include alkyls described in the substituent group A described later. A group, an aryl group, or a heterocyclic group.
Examples of the substituent represented by R ³ in the general formulas (2) to (4) include a substituent selected from the substituent group A described later.
_Examples of the substituent when R ₅₁ and R ₅₂ in the general formula (5) represent a substituent include a substituent selected from the substituent group A described later. R ₅₁ and R ₅₂ preferably each independently represent a hydrogen atom or a hydroxyl group. t is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
^Examples of the substituent in the case where R ⁶¹ , R ⁶² , R ⁶³ and R ^{64 in the} general formula (6) represent a substituent include a substituent selected from the substituent group A described later. R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently preferably represent a hydrogen atom or a hydroxyl group, more preferably a hydrogen atom. u and v are each independently preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
^Examples of the substituent when R ⁷¹ , R ⁷² and R ^{73 in the} general formula (7) represent a substituent include a substituent selected from the substituent group A described later. R ⁷¹ , R ⁷² and R ⁷³ each independently preferably represent a hydrogen atom or a hydroxyl group, and more preferably represent a hydrogen atom. w is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

In the general formulas (1) and (1-1) to (1-7), D ¹ represents a dye residue obtained by removing one arbitrary hydrogen atom from a dye. D ¹ is not limited as long as it exhibits the effects of the present invention, but represents a dye residue obtained by removing one hydrogen atom from a dye represented by any one of the following general formulas (M1) to (M4). More preferably. 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 n ²⁰¹ 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 n ³⁰¹ represents 0 or 1.

In general formula (M4), R ⁴⁰¹ to R ⁴⁰⁷ each independently represent a hydrogen atom or a substituent.

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), and R ⁴⁰¹ to R in general formula (M4) Examples of the substituent when R ⁴⁰⁷ represents a substituent include a substituent selected from the following substituent group A.

(Substituent group A)
The substituents included in Substituent Group A are shown below.
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a C1-C48, more preferably a C1-C24 linear, branched or cyclic alkyl group, Methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, A cyclohexyl group, a 1-norbornyl group, a 1-adamantyl group), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as a vinyl group, an allyl group, 3-butene- 1-yl group), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, An aryl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably having 3 to 38 carbon atoms, more preferably carbon number) 3-18 silyl groups, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably A linear, branched or cyclic alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methoxy group, Toxyl group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, cyclopentyloxy group, cyclohexyloxy group), aryloxy group (preferably having 6 to 48 carbon atoms, more preferably An aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group or 1-naphthoxy group), a heterocyclic oxy group (preferably having a carbon number of 1 to 32, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, For example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a trimethylsilyloxy group) , T-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group ( Preferably, it is an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, pivaloyloxy group, benzoyloxy group, dodecanoyloxy group), an alkoxycarbonyloxy group (preferably having a carbon number of 2 to 48, more preferably a linear, branched, or cyclic alkoxycarbonyloxy group having 2 to 24 carbon atoms, such as ethoxycarbonyloxy group, t-butoxycarbonyloxy group, cyclohexyloxycarbonyloxy group), aryloxycarbonyl An oxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyloxy group), a carbamoyloxy group (preferably 1 to 48 carbon atoms, more preferably Is a C1-C24 carba Yloxy group, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably carbon A sulfamoyloxy group having 1 to 32, more preferably 1 to 24 carbon atoms, such as N, N-diethylsulfamoyloxy group and N-propylsulfamoyloxy group), alkylsulfonyloxy group (preferably Is an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group, or an arylsulfonyloxy group (preferably having a carbon number). 6 to 32, more preferably 6 to 2 carbon atoms An arylsulfonyloxy group of, for example, a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), a linear, branched, or cyclic acyl group, for example, Formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, linear, branched, Or a cyclic alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), an aryloxycarbonyl Group (preferably having 7 to 32 carbon atoms, more preferably Is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group, N , N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N- Dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group) 2-ethylhexylamino group, cyclohexylamino group), anilino group (preferably Or an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as an anilino group or N-methylanilino group, or a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). A heterocyclic amino group such as a 4-pyridylamino group, a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms such as an acetamide group, a benzamide group, a tetradecanamide group, Pivaloylamide group, cyclohexaneamide group), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethylureido group, N-phenylureido group) ), An imide group (preferably an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, such as N— A succinimide group, N-phthalimido group), an alkoxycarbonylamino group (preferably a linear, branched or cyclic alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonyl Amino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 24 carbon atoms) Aryloxycarbonylamino group of, for example, phenoxycarbonylamino group), sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide group, butane Sulfonami Group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, For example, a phenylazo group, a 3-pyrazolylazo group), an alkylthio group (preferably a linear, branched, or cyclic alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylthio group, Ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably having 6 to 48 carbon atoms, more preferred) Is an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-benzo A thiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazolylthio group), an alkylsulfinyl group (preferably a linear, branched or cyclic alkyl having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). A sulfinyl group, for example, dodecanesulfinyl group), an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably an arylsulfinyl group having 6 to 24 carbon atoms, for example, a phenylsulfinyl group), an alkylsulfonyl group (preferably C1-C48, more preferably C1-C24 linear, branched, or cyclic alkylsulfonyl Group, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably Is an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyl group or 1-naphthylsulfonyl group, a sulfamoyl group (preferably having 32 or less carbon atoms, more preferably 24 carbon atoms). The following sulfamoyl groups include, for example, sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfa Moyl group ), Sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphinoyl An amino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino 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), and R ⁴⁰¹ to R in general formula (M4) When R ⁴⁰⁷ represents a substituent, the substituent may further have a substituent when the substituent is a substitutable group, and the substituent is a substituent selected from the above substituent group A. Group, and when it has two or more substituents, these substituents may be the same or different. R ¹⁰¹ to R ^{110 in} the general formula (M1), R ²⁰¹ to R ^{215 in} the general formula (M2), R ³⁰¹ to R ³¹⁷ in the general formula (M3), and R in the general formula (M4). ^{When 401} to R ⁴⁰⁷ represent a substituent, at least two of the substituents may be bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring, or an 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. When the substituent is substituted with two or more substituents, these substituents may be the same or different.

R ¹⁰¹ in the general formula (M1) is preferably a hydrogen atom or a hydroxyl group, and more preferably a hydroxyl group.
R ¹⁰² in formula (M1) is preferably a hydrogen atom, a halogen atom, a carboxyl group, or an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably a hydrogen atom, a halogen atom, or a carboxyl group, particularly preferably. Is a hydrogen atom, a bromine atom, or a carboxyl group.
R ¹⁰⁴ in formula (M1) is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. And particularly preferably an unsubstituted alkyl group having 1 to 8 carbon atoms.
R ¹⁰⁸ in the general formula (M1) is preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, Or a substituted or unsubstituted carbamoyl group.
R ¹⁰³ , R ¹⁰⁵ , and R ¹⁰⁶ in the general formula (M1) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 to 10 An aryl group, or a halogen atom, more preferably a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and particularly preferably a hydrogen atom.
R ¹⁰⁷ , R ¹⁰⁹ and R ¹¹⁰ in the general formula (M1) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 6 to 10 An aryl group, a halogen atom, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted carbamoyl group, more preferably a hydrogen atom or a halogen atom, particularly preferably. A hydrogen atom, a chlorine atom and a bromine atom.

R ²⁰¹ , R ²⁰⁵ , R ²⁰⁶ and R ²¹⁰ in formula (M2) are preferably each independently a hydrogen atom, a halogen atom or a hydroxyl group, more preferably a hydrogen atom.
R ²⁰² and R ²⁰⁹ in the general formula (M2) are preferably each independently a hydrogen atom, a halogen atom, a hydroxyl group, or a sulfo group, more preferably a hydrogen atom or a sulfo group, and particularly preferably hydrogen. Is an atom.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁷ and R ²⁰⁸ in the general formula (M2) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number. An aryl group having 6 to 18 carbon atoms, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, particularly preferably A hydrogen atom, a substituted or unsubstituted alkyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
R ²¹¹ in the general formula (M2) is preferably a carboxylate group (—CO ₂ ⁻ ), a sulfonate group (—SO ₃ ⁻ ), a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, or a substituted group Or an unsubstituted sulfamoyl group, more preferably a sulfonate group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group, particularly preferably a sulfonate group, An alkoxycarbonyl group;
R ²¹² , R ²¹³ , R ²¹⁴ and R ²¹⁵ in the general formula (M2) are preferably each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a carboxyl group, A substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a sulfo group, a substituted or unsubstituted sulfamoyl group, or a substituted or unsubstituted amino group, more preferably each independently a hydrogen atom or halogen atom. A carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a sulfo group, a substituted or unsubstituted sulfamoyl group, or a substituted or unsubstituted amino group, particularly preferably each independently Atom, substituted or unsubstituted alkoxy A rubonyl group, a substituted or unsubstituted carbamoyl group, a sulfo group, a substituted or unsubstituted sulfamoyl group, or a substituted or unsubstituted amino group.
R ²¹⁴ and R ²¹⁵ in formula (M2) are also preferably bonded to each other to form a ring.
X ²⁰¹ in the general formula (M2) is preferably a chlorine ion, an acetate ion, a triflate ion, a tetrafluoroborate ion, a tetrakis (pentafluorophenyl) borate ion, a perchlorate ion, or a bis (trifluoromethanesulfonyl) imide anion. More preferred are tetrakis (pentafluorophenyl) borate ion and bis (trifluoromethanesulfonyl) imide anion.
N201 in the general formula (M2) is preferably 0 or 1, more preferably 0.

In general formula (M3), R ³⁰¹ , R ³⁰² , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁷ , R ³⁰⁸ , R ³¹¹ , R ³¹² are preferably each independently a hydrogen atom, substituted or unsubstituted C 1-20. An alkyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a halogen atom, or a hydroxyl group, more preferably a hydrogen atom, a halogen atom, or a hydroxyl group, and particularly preferably a hydrogen atom.
R ³⁰³ , R ³⁰⁴ , R ³⁰⁹ and R ³¹⁰ in the general formula (M3) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number 6 Represents an aryl group having ˜20, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, particularly preferably a hydrogen atom. An alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 10 carbon atoms.
R ³¹³ in formula (M3) is preferably a carboxylate group, a sulfonate group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group, more preferably , Sulfonate group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted sulfamoyl group, particularly preferably sulfonate group and alkoxycarbonyl group.
R ³¹⁴ in the general formula (M3) is preferably a hydrogen atom, a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom, A halogen atom and a hydroxyl group, particularly preferably a hydrogen atom.
R ³¹⁵ in formula (M3) is preferably a hydrogen atom, a substituted or unsubstituted amino group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a sulfo group, substituted or unsubstituted A sulfamoyl group or a hydroxyl group, more preferably a hydrogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group. And particularly preferably a substituted or unsubstituted amino group, or a substituted or unsubstituted sulfamoyl group.
R ³¹⁶ and R ³¹⁷ in formula (M3) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, hydroxyl Or a halogen atom, more preferably a hydrogen atom, a halogen atom, or a hydroxyl group, and particularly preferably a hydrogen atom.
R ³¹⁶ and R ³¹⁷ in formula (M3) are also preferably bonded to each other to form a ring.
X ³⁰¹ in the general formula (M3) is preferably a chlorine ion, an acetate ion, a triflate ion, a tetrafluoroborate ion, a tetrakis (pentafluorophenyl) borate ion, a perchlorate ion, or a bis (trifluoromethanesulfonyl) imide anion. More preferred are tetrakis (pentafluorophenyl) borate ion and bis (trifluoromethanesulfonyl) imide anion.
N301 in the general formula (M3) is preferably 0 or 1, more preferably 0.

R ⁴⁰¹ in the general formula (M4) is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted acyl group. More preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and particularly preferably a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms.
R ⁴⁰² in formula (M4) is preferably a hydrogen atom or a substituted or unsubstituted amino group, more preferably a substituted or unsubstituted amino group, and particularly preferably a substituted or unsubstituted acylamino group. is there.
R ⁴⁰³ , R ⁴⁰⁶ and R ⁴⁰⁷ in formula (M4) are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted carbon number of 1 An alkoxy group having 1 to 20 carbon atoms or a halogen atom, more preferably a hydrogen atom, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, particularly preferably a hydrogen atom.
R ⁴⁰⁴ and R ⁴⁰⁵ in formula (M4) are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and more A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is preferred, and a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms is particularly preferred.

Specific examples of the dyes represented by the above general formula (M1), general formula (M2), general formula (M3) and general formula (M4) are shown below. Me represents a methyl group, Et represents an ethyl group, and i-Pr represents an isopropyl group.

The dye represented by the general formula (M1), the dye represented by the general formula (M2), the dye represented by the general formula (M3), and the dye represented by the general formula (M4) are conventionally known methods. (For example, Japanese Patent Publication No. 7-49583, Japanese Patent Publication No. 5-5257, Japanese Patent No. 5715380, WO2010 / 110199, WO2015 / 016265, etc.). The synthesis method is specifically illustrated in the examples.

(Molecular weight of dye polymer (P))
In the present invention, since the dye polymer (P) is used in a state of being dispersed in water, the dye polymer (P) has an optimum molecular weight range with respect to dispersibility. Re-aggregation hardly occurs. On the other hand, it is difficult to dissolve in water and an aqueous organic solvent as long as it is at least the lower limit of the optimum molecular weight range. Depending on the type of dye polymer (P) used, it is generally preferable to use a polymer having a weight average molecular weight of 3,000 to 2,000,000, preferably 3,000 to 1,000,000. Are more preferable, and those of 3,000 to 200,000 are particularly preferable.
The weight average molecular weight of the dye polymer (P) can be calculated from gel permeation chromatography (GPC) measurement. In this specification, unless otherwise specified, GPC is HLC-8220GPC (manufactured by Tosoh Corporation), and the column is measured with TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation), and the number average molecular weight. Was calculated by polystyrene conversion. The carrier may be appropriately selected, but NMP (N-methylpyrrolidone) was used as long as it was soluble.

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

The content of the repeating unit having a structure derived from the dye in the dye polymer (P) with respect to all repeating units is preferably 10 to 90% by mass, more preferably 25 to 90% by mass, and particularly preferably 50 to 90% by mass. 80% by mass. If the content rate of the repeating unit which has a structure derived from dye is 10 mass% or more, the coloring power per unit mass will improve and the dyeing density to a fabric will become high. Moreover, it is easy to adjust molecular weight to an appropriate range at the time of dye polymer synthesis as it is 90 mass% or less.

Hereinafter, repeating units other than the repeating unit having a structure derived from a dye that can be introduced into the dye polymer (P) will be described.

(Hydrophobic group-containing monomer)
Examples of the hydrophobic group-containing monomer include vinyl monomers such as styrene monomers, phenyl group-containing (meth) acrylates, (meth) acrylic acid alkyl esters, alkyl vinyl ethers, (meth) acrylonitrile; Urethane group-containing vinyl monomer formed from polyisocyanate and polyol or polyamine; epoxy group-containing vinyl monomer formed from epichlorohydrin and bisphenol; polyvalent carboxylic acid and polyalcohol etc. are formed from monomers Ester group-containing vinyl monomers; silicone group-containing vinyl monomers formed from organopolysiloxanes and the like.
Preferably, styrene, benzyl methacrylate, methyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-isocyanatoethyl methacrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate.

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

(Anionic group-containing monomer)
As the anionic group-containing monomer, the following unsaturated carboxylic acid monomer, unsaturated sulfonic acid monomer, unsaturated phosphoric acid monomer, or an anhydride or salt thereof can be used. Examples of the unsaturated carboxylic acid monomer include (meth) acrylic acid, crotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl esters of unsaturated dicarboxylic acid, and anhydrides and salts thereof. Is mentioned.
Acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl succinic acid are preferable.
Examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, sulfuric acid ester of 2-hydroxyalkyl (meth) acrylate, and salts thereof. Is mentioned.
Examples of the unsaturated phosphoric acid monomer include vinylphosphonic acid, phosphoric acid ester of hydroxyalkyl (meth) acrylate (2 to 6 carbon atoms), and (meth) acrylic acid alkylphosphonic acid.
Styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid are preferred.

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

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

Specific examples of the dye polymer (P) preferably used in the present invention are shown below, but are not limited thereto. L ¹ in * 1 positions bonded to the carbon atom of the polymer backbone, * 2 denotes respectively the coupling position with the D ^1, * 3 in the D ¹ represents a bonding position to L ^1. Me represents a methyl group, and Et represents an ethyl group.

<Aqueous dispersion of dye polymer (P)>
The aqueous dispersion of the dye polymer (P) contains at least water and [A] the dye polymer (P), and preferably contains [B] an aqueous organic solvent. In addition, depending on the method for producing the aqueous dispersion of the dye polymer (P), [C] either a low molecular surfactant or a high molecular dispersant is used in combination or not (so-called self-dispersing). It may be.

[A] Dye polymer (P)
In the present invention, the above dye polymer (P) 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 present invention, since a step of washing with water after printing is unnecessary, the dye polymer is a polymer that is substantially insoluble in water. In the aqueous dispersion used in the present invention, a polymer that is insoluble in water is dispersed as particles, and the particle size is preferably 50 to 500 nm. If the polymer is dissolved in water, the polymer is not present as particles in water.
Only one dye polymer can be used, or two or more dye polymers can be mixed and used in an arbitrary ratio.
Water is not particularly limited, and pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. Further, water sterilized by ultraviolet irradiation or addition of hydrogen peroxide can also be used. It is preferable to use ultrapure water as water.

(1-1) Dispersibility The dye polymer (P) is water-dispersed as a property of the dye polymer (P) itself during water dispersion, or by adsorption with a low molecular surfactant or a high molecular dispersant used in combination. It is easy to become familiar (easy to get wet), and prevents electrostatic particles (repulsive force) and steric repulsion from reaggregating the fine particles of the dye polymer, and has a function of suppressing sedimentation.

(1-2) Average particle diameter The dye polymer (P) is in the form of particles in the aqueous dispersion. The average particle size of the particulate dye polymer in the aqueous dispersion of the dye polymer (P) 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 directly printed by the ink jet method.
The value measured using the particle size distribution measuring apparatus (Nanotrack UPA EX150, the Nikkiso Co., Ltd. make, brand name) was used for the average particle diameter in this specification.

The content of the dye polymer (P) in the 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 dyed cloth can be obtained in printing while ensuring storage stability as an inkjet ink.
The content of water in the aqueous dispersion is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. Within this range, the 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.

[B] Aqueous organic solvent The aqueous organic solvent preferably has a water solubility at 25 ° C. of 10 g / 100 g-H ₂ O or more, more preferably 20 g / 100 g-H ₂ O, and water and an optional solvent. Those mixed in proportions are particularly preferred. Examples of the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, 1,2,6 -Hexanetriol, thioglycol, hexylene glycol, glycerin, diglycerin, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol monoethyl ether, Examples thereof include ethylene glycol monobutyl ether and acetonitrile. Preferred are trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, 2-pyrrolidone, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol monobutyl ether, more preferably ethylene. Glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, 2-pyrrolidone and ethylene glycol monobutyl ether are preferred, with ethylene glycol, glycerin and 2-pyrrolidone being particularly preferred.
The content of the aqueous organic solvent in the aqueous dispersion is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. Within this range, the stability of the aqueous dispersion and the ejection stability as an inkjet ink can be imparted.

[C] Low molecular surfactant or polymer dispersant As the low molecular surfactant or polymer dispersant, a low molecular surfactant or polymer dispersant having a hydrophobic group and an ionic group is preferable. And preferably have the following characteristics.

(2-1) Dispersibility The low molecular surfactant or polymer dispersant is added when dispersing the dye polymer (P), so that the low molecular surfactant or polymer dispersant becomes the dye polymer. Dye polymer fine particles adsorbed on the surface and blended (wet) with water, and ground by mechanical action, prevent re-aggregation of fine particles by electrostatic repulsion (repulsive force) and steric repulsion, and function to suppress sedimentation. Have.

(2-2) Molecular Weight In the case of a polymer type dispersant, there is an optimum molecular weight for the dispersion effect with respect to the dye polymer (P). It causes bridging and causes aggregation of the dye polymer. On the other hand, if the molecular weight is smaller than the optimum molecular weight, desorption from the dye polymer is likely to occur, and the effect as a dispersant is reduced. Further, when the molecular weight is small, the effect as a fixing agent after crosslinking is weakened. Accordingly, it is preferable to use a polymer type dispersant having a weight average molecular weight of 2,000 to 50,000. The weight average molecular weight of the polymeric dispersant is measured by the same method as the weight average molecular weight of the dye polymer.

(2-3) Structure and form The low molecular weight surfactant or polymer type dispersant is composed of a hydrophobic group (electrically neutral nonpolar group having low affinity with water) and an ionic group (electrical). It is preferable to have an ionic polar group having high affinity with water. The structure may be linear or branched. In the case of a high-molecular-weight surfactant, the structure may be random, alternating, periodic, or block, and may be a graft polymer designed with a trunk and branch structure.
The low molecular surfactant and the polymer dispersant can be used in any form of an aqueous solution, a dispersion, or an emulsion when mixed with water or an aqueous organic solvent.

(2-4) Formation Method and Obtaining Method For example, the following low molecular surfactants can be used.
Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. As an anionic surfactant, for example, fatty acid soap (for example, sodium oleate), N-acyl glutamate, alkyl sulfonate, alkyl benzene sulfonate, alkyl sulfoacetate, sulfated oil, higher alcohol sulfate ester And alkyl phosphate ester salts. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, and imidazolinium betaine. A suitable example is an amine oxide type such as N, N-dimethyl-N-alkylamine oxide.
Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid Examples include esters, propylene glycol fatty acid esters, and acetylene glycols. A suitable example is SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant. In addition, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. Those listed as surfactants in 308119 (1989) can also be used.
The content of the low molecular surfactant is preferably in the range of 0.001 to 5.0% by mass with respect to the total mass of the aqueous dispersion, and the surface tension of the aqueous dispersion is arbitrarily adjusted within this range. It is preferable to do.

The polymeric dispersant can be produced by copolymerizing a hydrophobic group-containing monomer and an ionic group-containing monomer. Each monomer may be used alone or in combination of two or more. The hydrophobic group-containing monomer and the ionic group-containing monomer are the same as the monomer of the copolymer component of the dye polymer (P) described above. As the polymeric dispersant, DISPERBYK-194N (trade name) manufactured by Big Chemie Japan, EFKA7422 (trade name) manufactured by BASF, and the like can also be used.
The content of the polymeric dispersant is preferably in the range of 0.001 to 50% by mass with respect to the total mass of the aqueous dispersion, and the surface tension of the aqueous dispersion can be arbitrarily adjusted within this range. Is preferred.

A method for producing an aqueous dispersion of a dye polymer (P) is as follows: (A) 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. After mixing with glass beads, zirconia beads, titania beads, or stainless steel balls, etc. A soluble polymerizable dye monomer, if necessary, a copolymerization monomer, and an emulsifier (surfactant) are mixed, and a polymerization initiator (usually a radical generator) that can be dissolved in water or an aqueous organic solvent is added thereto. There is a method using emulsion polymerization, and these can be suitably used.
In addition, a glycol solvent as a wetting agent, for example, ethylene glycol, propylene glycol, diethylene glycol, glycerin, polyethylene glycol, etc., and urea, hyaluronic acid, sucrose, etc. may be added to these dispersions as necessary. it can. In addition, the above-mentioned nonionic surfactants and anionic surfactants can be added as dispersion aids, but these surfactants are used in a small amount so as not to lower the performance as dispersion stability. It is preferable to mix.

<Inkjet ink>
In the printing method of the present invention, an ink-jet ink containing an aqueous dispersion of the dye polymer (P), a polymerizable compound, and a polymerization initiator is used.
The inkjet ink used in the printing method of the present invention is a dispersion liquid in which a dye polymer is dispersed in a liquid containing water. In addition, the dye polymer is in the form of particles in the inkjet ink, and the preferable average particle diameter of the particulate dye polymer is the same as that described above.

The content of the polymerizable compound in the inkjet ink is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass with respect to the total amount of the inkjet ink.

The content of the polymerization initiator in the ink-jet ink is preferably 0.01 to 35 parts by weight, more preferably 0.1 to 35 parts by weight, and still more preferably 0.00 with respect to 100 parts by weight of the polymerizable compound. It is contained in the range of 5 to 35 parts by mass. In addition, content of a polymerization initiator means the total amount which the polymerization initiator used.

The present invention also relates to an inkjet ink containing an aqueous dispersion of a dye polymer (P), a polymerizable compound, and a polymerization initiator. The inkjet ink is preferably used for textile printing.

The ink-jet ink used in the present invention preferably further contains water or an aqueous organic solvent. Moreover, you may contain components, such as another coloring agent, an organic solvent, surfactant, and various additives as needed.
The ink-jet ink containing the aqueous dispersion of the dye polymer of the present invention has excellent light resistance, so it can be used not only for fiber dyeing but also for paper media dyeing, plastic dyeing, paints, coatings, and building materials. Can do.

The inkjet ink used in the present invention may further contain a colorant (dye, pigment, etc.) other than the dye polymer (P). When other colorants are included, the content of the dye polymer (P) is preferably 50% by mass or more, more preferably 80% by mass or more, based on the total mass of the colorant including the dye polymer (P). Furthermore, it is preferable to contain only 100% by mass, that is, only the dye polymer (P).
The content of the colorant (including the dye polymer (P) and other colorants) in the inkjet ink is such that a good dyeing concentration is obtained, and considering the storage stability of the inkjet ink, The amount is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 12% by mass based on the mass.

The content of the dye polymer (P) in the inkjet ink is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 12% by mass with respect to the total mass of the inkjet ink. .
The water content in the inkjet ink is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 50 to 80% by mass.
The method for preparing the ink-jet ink is not particularly limited. For example, the ink-jet ink is prepared by mixing an aqueous dispersion of a dye polymer, a polymerizable compound, a polymerization initiator, and water or an aqueous organic solvent or other components as necessary. be able to.

<Organic solvent>
Examples of the organic solvent that can be contained in the inkjet ink used in the present invention include polyhydric alcohols (eg, ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene Glycol, triethylene glycol, tripropylene glycol, 1,2,4-butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 1,2-hexanediol, 1,5-pentane Diol, 1,2-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol , 3-Methyl-1,3-butanedio And 2-methyl-1,3-propanediol), amines (eg, ethanolamine, 2- (dimethylamino) ethanol, etc.), monohydric alcohols (eg, methanol, ethanol, butanol, etc.), Alkyl ethers of polyhydric alcohols (for example, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, And dipropylene glycol monomethyl ether), 2,2′-thiodiethanol, amides (for example, N, N-di) Sulfurformamide, etc.), sulfolane, dimethyl sulfoxide, 3-sulfolene-containing sulfur compounds, heterocycles (2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N- Ethyl morpholine) and acetonitrile. These may be used alone or in combination of two or more.
The organic solvent that can be contained in the inkjet ink used in the present invention is preferably the aforementioned aqueous organic solvent.
The content of the organic solvent in the inkjet ink is preferably 1% by mass to 60% by mass and more preferably 2% by mass to 50% by mass with respect to the total mass of the inkjet ink.

<Surfactant>
The inkjet ink used in the present invention can further use various surfactants from the viewpoint of enhancing storage stability, ejection stability, ejection accuracy, and the like. As the surfactant, any of cationic, anionic, amphoteric and nonionic surfactants can be used.

Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts.

Examples of the anionic surfactant include fatty acid soaps, N-acyl glutamates, alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfoacetates, sulfated oils, higher alcohol sulfates, and alkyl phosphates. Etc.

Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, and imidazolinium betaine. A suitable example is an amine oxide type such as N, N-dimethyl-N-alkylamine oxide.

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid Examples include esters, propylene glycol fatty acid esters, and acetylene glycols. A suitable example is Surfynol (trade name, manufactured by Air Products) which is an acetylene-based polyoxyethylene oxide surfactant.
In addition, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. Those listed as surfactants in 308119 (1989) can also be used.

When each of these surfactants is used, one surfactant may be used alone, or two or more surfactants may be mixed and used.
The content of the surfactant in the inkjet ink used in the present invention is preferably in the range of 0.001% by mass to 5.0% by mass with respect to the total mass of the inkjet ink. It is preferable to arbitrarily adjust the surface tension.

<Various additives>
The ink-jet ink used in the present invention may contain various other conventionally known additives. Examples of additives include pH adjusters such as acid bases and buffer solutions, fluorescent brighteners, surface tension adjusters, antifoaming agents, drying inhibitors, lubricants, thickeners, ultraviolet absorbers, anti-fading agents, Examples thereof include an antistatic agent, a matting agent, an antioxidant, a specific resistance adjusting agent, a rust preventive agent, an inorganic pigment, a reduction inhibitor, an antiseptic, an antifungal agent, a chelating agent, a sensitizer and a crosslinking agent.

(UV absorber)
As ultraviolet absorbers, they are described in JP-A-58-185777, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, JP-B-56 -21141, JP-A-10-88106, etc., cinnamic acid compounds, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10- Triazine compounds described in Japanese Patent No. 182621, Japanese National Publication No. Hei 8-501291, etc., Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used. When the inkjet ink contains an ultraviolet absorber, image storability can be improved.

(Anti-fading agent)
As an anti-fading agent, various organic and metal complex anti-fading agents can be used. Examples of organic fading inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex include a nickel complex and a zinc complex. More specifically, Research Disclosure No. No. 17643, VII, I and J, No. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. Included in the general formulas and compound examples of the compounds described in the patent cited in US Pat. No. 15162, and representative compounds described in JP-A-62-215272, pages 127 to 137, and US Pat. No. 5,356,443. Can be used. When the ink-jet ink contains an anti-fading agent, image storability can be improved.

(Preservatives and antifungal agents)
The ink-jet ink used in the present invention may contain at least one of a preservative and an antifungal agent in order to maintain long-term storage stability of the ink. When the ink-jet ink contains a preservative or an antifungal agent, long-term storage stability can be enhanced. Examples of antiseptics and antifungal agents include aromatic halogen compounds (for example, Priventol CMK; manufactured by LANXESS, trade name), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (For example, Proxel GXL; manufactured by Arch Chemicals, trade name), sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one, And salts thereof.
A preservative and an antifungal agent may be used individually by 1 type, and may use 2 or more types together. When the inkjet ink contains a preservative and an antifungal agent, the content of the antiseptic and the antifungal agent is preferably 0.02% by mass to 1.00% by mass with respect to the total mass of the inkjet ink.

(Anti-drying agent)
As the drying inhibitor, an aqueous organic solvent having a vapor pressure lower than that of water can be suitably used. When the inkjet ink contains an anti-drying agent, clogging due to drying of the ink can be prevented at the ejection port of the nozzle of the ejection head that ejects the ink when used for inkjet recording.
Specific examples of the drying inhibitor include, for example, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol. , Acetylene glycol derivatives, glycerin, polyhydric alcohols typified by trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) Lower alkyl ethers of polyhydric alcohols such as ether, heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N-ethylmorpholine, Horan, dimethyl sulfoxide, and sulfur-containing compounds such as sulfolane, diacetone alcohol, and polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
Moreover, a drying inhibitor may be used individually by 1 type, and may use 2 or more types together. When the inkjet ink contains a drying inhibitor, the content of the drying inhibitor is preferably 10% by mass to 50% by mass with respect to the total mass of the inkjet ink.

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

(Surface tension modifier and antifoaming agent)
Examples of the surface tension adjusting agent include various surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants. Preferred examples of the surfactant are the same as those exemplified in the above-mentioned surfactant column.
As the antifoaming agent, fluorine-based and silicone-based compounds are preferable.

The ink jet ink used in the present invention is preferably adjusted to have a surface tension of 20 mN / m to 70 mN / m, and more preferably 25 mN / m to 60 mN / m. The viscosity of the inkjet ink is preferably adjusted to 40 mPa · s or less, more preferably adjusted to 30 mPa · s or less, and particularly preferably adjusted to 20 mPa · s or less.
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.

(Chelating agent)
The chelating agent is preferably used for the purpose of preventing the generation of precipitates such as precipitates in the ink-jet ink, and for the purpose of improving storage stability and clogging recovery. When dyes are used as colorants for inkjet inks, the metal ions (Ca, Mg, Si, Fe, etc.) contained in the ink can cause precipitation and reduce clogging recovery. It is known that it is necessary to manage below the amount. In addition, when a copper complex dye is used, even if the amount of metal ions is controlled, if the amount of free copper ions is not controlled, the occurrence of precipitates and a reduction in clogging recovery may be observed. It is known (see JP 2000-355665 A, JP 2005-126725 A, etc.).
Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, uramildiacetic acid, and metal salts thereof (for example, sodium salt).

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

[Method for producing printed matter]
The present invention also relates to a method for producing a printed material including the steps (A) and (B).
It is preferable that the method for producing a printed material of the present invention further includes the step (C).

<Base material>
The printing method of this invention provides the said inkjet ink on a base material.
Although there is no restriction | limiting in particular as a base material used for the printing method of this invention, Permeable base materials, such as normal papers, such as uncoated paper and a coated paper, and the cloth of various fiber types, are mentioned. In addition, since the polymerizable compound contained in the inkjet ink is polymerized and functions as a binder between the substrate and the dye polymer, the printing method of the present invention can form a non-permeable substrate having a high affinity with the polymerizable compound. It is also possible to use it.
As the non-penetrating substrate, a known substrate can be used without limitation, and examples thereof include synthetic resin, rubber, resin-coated paper, and metal.
As the synthetic resin, known synthetic resins can be used without limitation. For example, polyvinyl chloride; polystyrene; polyurethane; polyolefin such as polyethylene and polypropylene; polyester such as polyethylene terephthalate and polybutadiene terephthalate; Polyamides such as nylon; acrylic resins, polycarbonates, acrylonitrile-butadiene-styrene copolymers, diacetates, triacetates, polyimides, cellophanes, celluloids, and the like.

Thus, the printing method of the present invention can be applied to various base materials, but is particularly suitable when a fabric is used as the base material.

-Fabric-
Examples of the fabric to which the printing method and the colored fabric manufacturing 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.
Apparel includes T-shirts, trainers, jerseys, pants, sweatsuits, dresses, blouses and the like. It is also suitable for bedding and handkerchiefs.

Since the printed matter produced by the printing method of the present invention or the printed matter production method has an excellent effect in any of the characteristics of pinning, color development, and friction resistance, the printing method of the present invention and the printed matter production method , And inkjet inks are of great value.

〔ink cartridge〕
The present invention also relates to an ink cartridge filled with the inkjet ink of the present invention, that is, an inkjet ink containing an aqueous dispersion of a dye polymer (P), a polymerizable compound, and a polymerization initiator.

[Printed matter]
The present invention also relates to a printed matter having an image including a dye polymer having a repeating unit including a structure derived from a dye and a polymer different from the dye polymer on at least a part of the surface of the substrate.
The polymer different from the dye polymer is preferably a polymer of the polymerizable compound.

[Colored fabric]
The present invention also relates to a colored fabric having an image including a dye polymer having a repeating unit including a structure derived from a dye and a polymer different from the dye polymer on at least a part of the surface of the fabric.

(Synthesis Example 1)
[Synthesis of Dye Polymer (Y-2-1)]
Exemplary compound (Y-2-1) was synthesized according to the following scheme.

10 mL of N-methylpyrrolidone (NMP) was added to a 100 mL three-necked flask, and the internal temperature was raised to 85 ° C. To the above 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, manufactured by Wako Pure Chemical Industries), V-601 ( A solution prepared by dissolving 0.126 g of Wako Pure Chemical Industries, Ltd. (trade name) and 0.443 g of 1-dodecanethiol (product of Wako Pure Chemical Industries) 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 room temperature, poured into 500 mL of water to precipitate crystals, and the crystals are separated by filtration. A yellow powder of Y-2-1) was obtained. The yield of exemplary compound (Y-2-1) was 9.8 g. The absorption maximum wavelength of the ultraviolet-visible absorption spectrum in a dilute solution of Exemplified Compound (Y-2-1) in tetrahydrofuran (THF) was 441 nm. The weight average molecular weight (Mw) of the exemplified compound (Y-2-1) as measured by gel permeation chromatography (GPC) was 10,500 (polystyrene conversion).

Other dye polymers were synthesized according to Synthesis Example 1 above.

(Synthesis Example 2)
[Synthesis of Amphiphilic UV Curing Resin (B1)]
(1) Synthesis of polyethylene glycol atom transfer radical polymerization (ATRP) macroinitiator:
20 g (0.01 mol) of poly (ethylene glycol) monomethyl ether (number average molecular weight 2000) and 2.0 g (0.02 mol) of triethylamine were dissolved in 140 mL of anhydrous tetrahydrofuran (THF). The solution was allowed to cool slightly in an ice bath and 8.6 mL (0.07 mol) of 2-bromoisobutyryl bromide was added slowly. The solution was then warmed to 20 ° C. and stirred for 24 hours. The mixture was poured into water and extracted with methylene chloride. The obtained extract was washed in turn with a 1 mol / L hydrochloric acid aqueous solution and a 1 mol / L sodium hydroxide aqueous solution, dried over magnesium sulfate, and the solvent was removed under reduced pressure. The obtained crude product was dissolved in a minimum amount of methylene chloride capable of being dissolved, diethyl ether was added for precipitation, and the precipitate was filtered to obtain a white solid.
(2) Synthesis of poly (ethylene glycol) -poly (styrene-co-acrylic acid):
1.1 molar equivalents of N, N, N ′, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 1.1 molar equivalents of copper (I) bromide, 5 molar equivalents of styrene and 5 molar equivalents of acrylic The acid was dissolved in THF and 1 molar equivalent of polyethylene glycol ATRP macroinitiator was added. This was degassed at 20 ° C. using argon gas for 15-20 minutes and then heated at 60 ° C. for 8 hours. This was poured into THF containing 10% methanol. The precipitated polymer was filtered on silica gel to remove copper bromide. Further, the obtained polymer was dialyzed against water for 48 hours and freeze-dried.
(3) Synthesis of poly (ethylene glycol) -poly (styrene-co-4-hydroxybutyl acrylate glycidyl ether-modified acrylic acid):

11 molar equivalents of poly (ethylene glycol) -poly (styrene-co-acrylic acid) were dissolved in methyl ethyl ketone. To this solution, 5 molar equivalents of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Chemical Co., Ltd.) was added. To this, 5000 ppm of tetrabutylammonium chloride and 2000 ppm of hydroquinone monomethyl ether were added and reacted at 50 ° C. for 10 hours. After completion of the reaction, it was washed with water, and methyl ethyl ketone was removed using an evaporator.
The resulting composite was examined using an infrared spectrophotometer the disappearance of the characteristic absorption 1250 cm ^-1 and 950 ~ 800 cm ^-1 of epoxide groups, and confirmed the presence of characteristic absorption 810 cm ^-1 for vinyl group . In other words, it was confirmed that poly (ethylene glycol) -poly (styrene-co-4-hydroxybutyl acrylate glycidyl ether-modified acrylic acid) was synthesized from poly (ethylene glycol) -poly (styrene-co-acrylic acid). It was. Moreover, the weight average molecular weight (Mw) in gel permeation chromatography (GPC) measurement was 89,600 (polystyrene conversion).
Poly (ethylene glycol) -poly (styrene-co-4-hydroxybutyl acrylate glycidyl ether-modified acrylic acid) is represented by the following formula.

(Synthesis Example 3)
Synthesis of polymerizable polymer (B2) [poly (benzyl methacrylate-co-glycidyl methacrylate-modified methacrylic acid):

To a three-necked flask, 75 g of propylene glycol monomethyl ether was added, and the internal temperature was raised to 85 ° C. under a nitrogen atmosphere. A solution prepared by dissolving 54 g of benzyl methacrylate, 27.6 g of methacrylic acid, and 4.5 g of a polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) in 75 g of propylene glycol monomethyl ether was added over 2 hours. The solution was slowly added dropwise while maintaining the internal temperature at 84 to 86 ° C. After completion of the dropwise addition, the mixture was reacted for 1 hour at an internal temperature of 85 ° C., and 1.5 g of V-601 was added. After reacting at an internal temperature of 85 ° C. for 1 hour, the reaction was carried out at 100 ° C. for 120 minutes to adjust the internal temperature to 90 ° C. To this was added 0.2 g of p-methoxyphenol, then 1.5 g of dodecyldimethylamine and 19.2 g of glycidyl methacrylate, and reacted at 90 ° C. for 6 hours. The resulting reaction solution was cooled to room temperature and reprecipitated using water. The resulting composite was examined using an infrared spectrophotometer the disappearance of the characteristic absorption 1250 cm ^-1 and 950 ~ 800 cm ^-1 of epoxide groups, and confirmed the presence of characteristic absorption 810 cm ^-1 for vinyl group . That is, it was confirmed that poly (benzyl methacrylate-co-glycidyl methacrylate-modified methacrylic acid was synthesized, and the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) was 43,600 (polystyrene conversion). Met.
The polymerizable polymer (B2) [poly (benzyl methacrylate-co-glycidyl methacrylate-modified methacrylic acid)] is represented by the following formula.

(Example 1)
(Preparation of aqueous dispersion of dye polymer)
0.25 g of exemplified compound (Y-2-1), 10 g of zirconia beads (product name: YTZ ball, diameter: 0.1 μm), 0.05 g of sodium oleate, 0.5 g of glycerin, and 4.2 g of ultrapure water Was added and dispersed for 10 hours at a rotation speed of 400 rpm (rotation 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 (1).

[Preparation of inkjet ink]
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 an inkjet ink (A1).
Dye polymer aqueous dispersion (1) 30g
Amphiphilic UV curable resin (B1) 6g
Polymerization initiator IRGACURE TPO (BASF, trade name) 2g
Ethylene glycol 6g
Surfactant BYK-349 (Bic Chemie, trade name) 2g
34g of ultrapure water

<Process (A): Inkjet printing, Process (B): Light irradiation>
The prepared ink-jet ink (A1) was filled into an ink cartridge, and pinned using an ink-jet printer (Calario PX-045A, trade name, manufactured by Seiko Epson Corporation) remodeled so that the LED could be mounted. Printing was performed on a polyvinyl chloride film (IMAGin JT 5829 R, manufactured by MACTAC) as a base material by a method including a step of performing irradiation of 100 mJ / cm ² after 02 seconds.

<Step (C): Heat treatment>
The printed matter obtained above was dried at 20 ° C. for 24 hours, and then heat-pressed (trade name: tabletop automatic flat press machine AF-54TEN type, manufactured by Asahi Textile Machinery Co., Ltd.) at a temperature of 120 ° C. and a pressure of 0.20 N / A heat treatment was performed at cm ² for 60 seconds to obtain a printed matter.

(Example 2)
A printed matter (colored fabric) was obtained in the same manner as in Example 1 except that the base material in Example 1 was changed to a polyester fabric (polyester tropical (manufactured by Teijin), color dye company, product code A02-01019).

(Example 3)
A printed matter (colored fabric) was obtained in the same manner as in Example 1 except that the base material in Example 1 was changed to a cotton fabric (with cotton broad sill, manufactured by Color Dyeing Co., Ltd., product code A02-01002).

Example 4
A printed material (Example 1) except that the base material in Example 1 was changed to a polyester 65% cotton 35% blend (mixed polyester 65 / cotton 35 broad, manufactured by Color Dye, product code A02-01030). A colored cloth) was obtained.

(Example 5)
A printed matter was obtained in the same manner as in Example 1 except that the type of the dye polymer in Example 1 was changed to the exemplary compound (Y-1-3).

(Example 6)
A printed matter was obtained in the same manner as in Example 1 except that the type of the dye polymer in Example 1 was changed to (Y-2-2).

(Example 7)
A printed matter was obtained in the same manner as in Example 1 except that the type of the dye polymer in Example 1 was changed to the exemplary compound (B-2-2).

(Example 8)
A printed matter was obtained in the same manner except that the amphiphilic UV curable resin (B1) of Example 1 was changed to the polymerizable polymer (B2).

Example 9
A printed matter was obtained in the same manner except that the amphiphilic UV curable resin (B1) of Example 1 was changed to a water-soluble polyfunctional monomer FAM-402 (trade name, manufactured by FUJIFILM Corporation).

(Example 10)
A printed matter was obtained in the same manner except that the amphiphilic UV curable resin (B1) of Example 1 was changed to a water-soluble bifunctional monomer FAM-201 (trade name, manufactured by FUJIFILM Corporation).

(Example 11)
A printed matter was obtained in the same manner except that the amphiphilic UV curable resin (B1) of Example 1 was replaced with a water-soluble monopolyfunctional monomer FAM-101 (trade name, manufactured by FUJIFILM Corporation).

(Example 12)
A colored fabric was obtained in the same manner except that the dispersion time of the dye polymer (Y-2-1) of Example 1 was changed from 10 hours to 30 minutes. A slight print image defect was observed in the obtained colored fabric.

(Comparative Example 1)
20 g of poly (ethylene glycol) -poly (styrene-co-4-hydroxybutyl acrylate glycidyl ether-modified acrylic acid), 4 g of polymerization initiator IRGACURE TPO (trade name, manufactured by BASF), and 5 g of pigment solid content Silicone Yellow L 1912 (manufactured by Evonik Degussa) was added, added to 20 g of water, heated to 40 ° C. and mixed. After mixing, the mixture was subjected to ultrasonic mixing for 1 hour at a frequency of 19.9 kHz using a homogenizer S-250D (manufactured by BRANSON) while cooling the vessel with ice. After ultrasonic mixing, 51 g of water was gradually added thereto to prepare an amphiphilic block polymer emulsion containing the photopolymerization initiator and the pigment, that is, a photopolymerizable polymer micelle solution. The prepared photopolymerizable polymer micelle solution was mixed with the following components to prepare an inkjet ink (R1).

50 g of photopolymerizable polymer micelle solution
Propylene glycol 6g
1,2-hexanediol 3g
Surfactant BYK-349 (Bic Chemie, trade name) 2g
Tripropanolamine 0.5g
38.5g of ultrapure water

Printing was performed by performing steps (A), (B), and (C) in the same manner as in Example 1 except that the inkjet ink (A1) in Example 1 was changed to inkjet ink (R1).

The printed materials of Examples and Comparative Examples were evaluated as follows.
・ Pinning property:
A: No aggregation unevenness, B: Aggregation unevenness, C: No pinning (dots blur)
Color development: Visual Density (visible density) value when the reflection density was measured using a spectrocolorimeter Xrite939 (trade name, manufactured by X-Rite) under the conditions of a viewing angle of 2 °, a measuring range of 4 mmΦ, and an A light source. Measurements were made and evaluated as follows.
A: Reflection density is 1.2 or more, B: Reflection density is 1.0 or more and less than 1.2, C: Reflection density is less than 1.0 ・ Friction resistance: Japanese Industrial Standard (JIS) L0849: 2013, against friction Dye fastness test method (Friction tester type II (Gakushin type) method)
In addition, evaluation of friction resistance was evaluated by a series. The higher the series, the better the friction resistance.

In addition, the average particle diameter of the dye polymer shown in Table 1 below indicates a measured value of the average particle diameter in the aqueous dispersion of each prepared dye polymer.

As is apparent from the above results, it is clear that the printing method according to the embodiment of the present invention gives a printed matter excellent in pinning property, color development property, and abrasion resistance.

When the printed material was a colored cloth, the colored cloth was evaluated by the following method.
The evaluation of the colored fabric is a series performed as follows. The higher the series, the better the color fastness.
Washing resistance: Japanese Industrial Standard (JIS) L0844: 2011, Dye fastness test method for washing (A-2 test)
-Sweat resistance: JIS L0848: 2004, Dye fastness test method for sweat (acidic and alkaline)
-Friction resistance: JIS L0849: 2013, Dye fastness test method for friction (Friction tester type II (Gakushin type) method)
-Dry cleaning resistance: JIS 0860: 2008, Dye fastness test method for dry cleaning (A-2 test)

As is apparent from the above results, it can be seen that the printing method according to the embodiment of the present invention gives a colored cloth having excellent image fastness.

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 August 31, 2016 (Japanese Patent Application No. 2016-170037), the contents of which are incorporated herein by reference.

Claims

A printing method comprising the following steps (A) and (B).
Step (A): A step of applying an ink jet ink containing an aqueous dispersion of a dye polymer (P) having a repeating unit containing a structure derived from a dye, a polymerizable compound, and a polymerization initiator to the substrate by an ink jet method. (B): Light irradiation process
Furthermore, the printing method of Claim 1 including a process (C) heat processing process.
The printing method according to claim 1 or 2, wherein the substrate is a fabric.
The printing method according to claim 2, wherein the temperature of the heat treatment in the step (C) is 50 ° C or higher and lower than 250 ° C.
The dye polymer (P) in the aqueous dispersion is a particulate dye polymer, and the average particle diameter of the particulate dye polymer is 50 to 500 nm. Printing method.
The printing method according to any one of claims 1 to 5, wherein the dye polymer (P) has a weight average molecular weight of 3,000 to 200,000.
The printing method according to any one of claims 1 to 6, wherein the content of the polymerizable compound is 1 to 30% by mass with respect to the total amount of the inkjet ink.
The manufacturing method of printed matter including the following process (A) and (B).
Step (A): A step of applying an ink jet ink containing an aqueous dispersion of a dye polymer (P) having a repeating unit containing a structure derived from a dye, a polymerizable compound, and a polymerization initiator to the fabric by an ink jet method. B): Light irradiation process
Furthermore, the manufacturing method of the printed matter of Claim 8 including a process (C) heat processing process.
An inkjet ink containing an aqueous dispersion of a dye polymer (P) having a repeating unit containing a structure derived from a dye, a polymerizable compound, and a polymerization initiator.
The inkjet ink according to claim 10, which is used for textile printing.
An ink cartridge filled with the inkjet ink according to claim 10 or 11.
Printed matter having an image including a dye polymer having a repeating unit including a structure derived from a dye and a polymer different from the dye polymer on at least a part of the surface of the substrate.
A colored cloth having an image including a dye polymer having a repeating unit including a structure derived from a dye and a polymer different from the dye polymer on at least a part of the surface of the cloth.