WO2019058990A1

WO2019058990A1 - Ink composition, method for manufacturing same and image formation method

Info

Publication number: WO2019058990A1
Application number: PCT/JP2018/033087
Authority: WO
Inventors: 一郎小山; 昭太鈴木; 憲晃佐藤
Original assignee: 富士フイルム株式会社
Priority date: 2017-09-25
Filing date: 2018-09-06
Publication date: 2019-03-28
Also published as: JPWO2019058990A1; JP6938652B2

Abstract

An ink composition which contains water and particles comprising a polymer, said polymer being a urethane polymer, a urea polymer or a (meth)acrylic polymer and having a gelled group which is a product of a reaction between an active hydrogen group-containing gelling agent and an isocyanate group; a method for manufacturing the ink composition; and an image formation method.

Description

Ink composition and method for producing the same, and image forming method

The present disclosure relates to an ink composition, a method of producing the same, and an image forming method.

In the field of ink compositions, an aqueous dispersion of gel particles may be used, which comprises water as the liquid component.
For example, in Patent Document 1, a three-dimensional crosslinked structure including a thioether bond and an ethylenic double bond can be formed as an aqueous dispersion of gel particles capable of forming a film having both hardness and flexibility and having excellent redispersibility. There is disclosed an aqueous dispersion of gel particles in which gel particles having a hydrophilic group and containing a photopolymerization initiator are dispersed in water. Patent Document 1 also discloses that an aqueous dispersion of gel particles is used for ink jet recording.

Further, Patent Document 2 describes a film-forming material, a polyether-modified silicone oil, water, and the like as an ink composition for ink jet recording which is excellent in all of solid filling property, storage stability, and abrasion resistance. An ink composition for ink jet recording is disclosed, which contains a polyether-modified silicone oil and is soluble in a solvent having a SP value lower limit of 8.5 or less and an upper limit of 18.0 or more.

Patent Document 1: International Publication No. 2016/136113 Patent Document 2: Japanese Patent Application Publication No. 2014-5421

By the way, in general, in an ink film formed using an ink containing water as a liquid component, compared to an ink film formed using an ink containing a polymerizable monomer and / or an organic solvent as a liquid component, It tends to be difficult to remove the liquid component from the ink film. For this reason, an image formed using an ink containing water as a liquid component may be inferior in scratch resistance.
Therefore, it may be required to improve scratch resistance to an image formed using an ink containing water as a liquid component.

An object of the present disclosure is to provide an ink composition capable of forming an image excellent in scratch resistance, a method for producing the same, and an image forming method using the ink composition.

The specific means for solving the said subject contains the following aspects.
<1> with water,
Particles comprising a polymer having a gelling group which is a urethane polymer, a urea polymer or a (meth) acrylic polymer and which is a reaction product of a gelling agent having an active hydrogen group and an isocyanate group;
An ink composition containing

<2> The ink composition according to <1>, wherein the gelling group is a group represented by the following formula (G).

In formula (G), n ^G represents 1 or 2, R ^U represents a urethane group, a urea group, a thiourethane group, or a thiourea group, and L ^G represents a single bond or a divalent linking group. , * Represents a bonding position.
In the formula (G), R ^G is a polysaccharide, a protein, an acrylic resin, a vinyl resin, or a hydrogelator which is a polyoxyalkylene compound represented by the formula (1) when n ^G is 1. It represents a residue from which one hydrogen atom has been removed, or a monovalent hydrophobic group.
In formula (G), when n ^G is 2, R ^G represents a residue obtained by removing two hydrogen atoms from the above hydrogelator, or represents a divalent hydrophobic group.
In formula (1), n and m each independently represent an integer of 2 or more, p represents an integer of 0 or more, L represents an alkylene group having 3 or more carbon atoms, and R is a hydrogen atom , An alkyl group or an aryl group.

<3> The hydrogel forming agent is a polysaccharide or a polyoxyalkylene compound represented by the formula (1),
The monovalent hydrophobic group is a linear alkyl group having 10 or more carbon atoms,
The ink composition as described in <2> whose bivalent hydrophobic group is a C10 or more linear alkylene group.
<4> The hydrogelator is a polysaccharide,
The monovalent hydrophobic group is a linear alkyl group having 16 or more carbon atoms,
The ink composition as described in <2> or <3> whose bivalent hydrophobic group is a C16 or more linear alkylene group.
<5> The ink composition according to any one of <2> to <4>, wherein R ^U in the formula (G) is a urea group.
<6> The ink composition according to any one of <1> to <5>, wherein the gelling group is a monovalent group.
<7> The polymer is a linear polymer,
The ink composition according to <6>, wherein the gelling group is disposed at the end of the main chain of the linear polymer.
<8> The ink composition according to any one of <1> to <7>, wherein the particles contain a polymerizable monomer.
<9> The ink composition according to any one of <1> to <8>, wherein the polymer has a polymerizable group.
<10> The ink composition according to any one of <1> to <9>, which is used as an inkjet ink.
<11> A method of producing the ink composition according to any one of <1> to <10>,
A method for producing an ink composition comprising the step of forming particles by mixing and emulsifying an oil phase component containing an organic solvent and a polymer, and an aqueous phase component containing water.
<12> forming an ink film by applying the ink composition according to any one of <1> to <10> on a substrate;
Heating the ink film;
An image forming method including:

According to the present disclosure, an ink composition capable of forming an image excellent in scratch resistance, a method for producing the same, and an image forming method using the ink composition are provided.

It is a figure which shows the character image used for evaluation of the definition of the image in an Example.

In the present specification, a numerical range indicated by using “to” means a range including numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. Means
In the numerical range described step by step in the specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit in the numerical range described in the other stepwise Also, they may be replaced with the values shown in the embodiments.
In the present specification, the term "step" is not limited to an independent step, and may be included in the term if the intended purpose of the step is achieved even if it can not be clearly distinguished from other steps. Be
In the present specification, “*” in the chemical formula represents a bonding position.

In the present specification, the concept of “image” encompasses not only pattern images (eg, characters, symbols, or figures) but also solid images.
In the present specification, “light” is a concept including active energy rays such as γ rays, β rays, electron beams, ultraviolet rays, visible rays and the like.
In the present specification, ultraviolet light may be referred to as "UV (Ultra Violet) light".
In the present specification, light generated from a light emitting diode (LED) light source may be referred to as “LED light”.
In the present specification, “(meth) acrylic polymer” is a concept including both acrylic polymer and methacrylic polymer, and “(meth) acrylic acid” is a concept including both acrylic acid and methacrylic acid. The term "(meth) acrylate" is a concept including both acrylate and methacrylate, and the term "(meth) acryloyl group" is a concept including both an acryloyl group and a methacryloyl group.
In the present specification, the polyoxyalkylene group, the amido group, the urea group and the urethane group mean a polyoxyalkylene bond, an amido bond, a urea bond and a urethane bond, respectively.

[Ink composition]
The ink composition of the present disclosure (hereinafter, also simply referred to as “ink”) is a reaction of water, a urethane polymer, a urea polymer, or a (meth) acrylic polymer, and a gelling agent having an active hydrogen group and an isocyanate group. And particles containing a polymer having a gelling group (hereinafter, also referred to as "specific particles").

As described above, in general, an ink film formed using an ink containing water as a liquid component is compared to an ink film formed using an ink containing a polymerizable monomer and / or an organic solvent as a liquid component. Therefore, it tends to be difficult to remove the liquid component from the ink film. For this reason, an image formed using an ink containing water as a liquid component may be inferior in scratch resistance.

Regarding the points described above, according to the ink of the present disclosure, an image excellent in scratch resistance can be formed.
The reason why such an effect is exerted is presumed as follows, but the ink of the present disclosure is not limited by the following reasons.

When the ink of the present disclosure is applied onto a substrate to form an ink film, the formed ink film contains specific particles that are components in the ink. The specific particles include a polymer having a gelling group which is a reaction product of a gelling agent having an active hydrogen group and an isocyanate group.
By heating the ink film, it is considered that the gelling function of the gelling group is exhibited and the ink film is thickened (i.e., gelation).
Therefore, when the ink of the present disclosure is applied onto a substrate to form an ink film and the ink film is heated (including the case where the ink of the present disclosure is applied to a heated substrate to form an ink film) The same applies hereinafter), it is considered that the strength of the ink film can be effectively enhanced by the thickening of the ink film described above. As a result, it is considered that the scratch resistance of the ink film (i.e., the image) is improved.

Also, in general, in an image formed using an ink containing water as a liquid component, compared with an image formed using an ink containing a polymerizable monomer and / or an organic solvent as a liquid component, It tends to be inferior in definition. The reason for this is that in ink droplets formed using an ink containing water as a liquid component, unintended ink droplet coalescence may occur on the substrate because it is difficult to remove the liquid component from the ink droplets. It is thought that there is.
In this regard, according to the ink of the present disclosure, an image with excellent definition can be formed.
The reason why such an effect is exerted is considered to be that unintended ink droplet coalescence on the substrate is suppressed by the above-described thickening of the ink film (here, thickening of the ink droplets).
Here, the ink droplet is an aspect of the ink film.

In the present specification, the active hydrogen group means a hydroxy group, a primary amino group, a secondary amino group or a thiol group.

The thickening mechanism of the ink film described above is considered to be different depending on the type of gelling agent having an active hydrogen group (hereinafter, also referred to as “specific gelling agent”) for forming a gelling group.
Specific gelling agents (ie, gelling agents having active hydrogen groups) include, for example, hydrogelators having active hydrogen groups and amphiphilic gelling agents having active hydrogen groups.

As used herein, the hydrogel agent means a compound having a function of forming a hydrogel upon heating.
As used herein, the hydrogel agent having an active hydrogen group means a hydrogel agent, which is a compound having an active hydrogen group.
The hydrogel forming agent has two or more types of sites having different degrees of hydrophilicity in the compound in order to exert the function of forming a hydrogel.
Therefore, the degree of hydrophilicity in the compound is almost uniform, polyethylene glycol (that is, homopolymer of ethylene glycol), polypropylene glycol (that is, homopolymer of propylene glycol), polyethylene glycol monomethyl ether (PEGME; described later) Comparative Example 1) and the like do not correspond to the hydrogel forming agent. These are merely hydrophilic polymers and do not have the function of forming a hydrogel.
On the other hand, a polyoxyalkylene compound (for example, ethylene glycol-propylene glycol copolymer) represented by the formula (1) or the formula (1A) described later, which has two or more kinds of sites having different degrees of hydrophilicity, It corresponds to a hydrogel forming agent, and also corresponds to a hydrogel forming agent having an active hydrogen group.
As a hydrogel forming agent having an active hydrogen group, in addition to the polyoxyalkylene compound represented by the formula (1) or the formula (1A) described later, polysaccharides, proteins, an acrylic resin having an active hydrogen group, an active hydrogen group And vinyl resins having the same.

In the present specification, the amphiphilic gelling agent having an active hydrogen group means a compound having an active hydrogen group and a hydrophobic group.
In the present specification, a hydrophobic group means a group capable of aggregating to form a hydrophobic segment. This hydrophobic segment becomes a gel.
As the hydrophobic group in the present specification,
As a monovalent hydrophobic group, an alkyl group having 4 or more carbon atoms, an alkenyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an alkoxyalkylene oxy group containing an alkylene group having 3 or more carbon atoms in the structure, a structure An alkoxypolyalkyleneoxy group containing an alkylene group having 3 or more carbon atoms, a hydroxyalkyleneoxy group containing an alkylene group having 3 or more carbon atoms in the structure, and a hydroxypolyalkyleneoxy group containing an alkylene group having 3 or more carbon atoms in the structure Groups, etc.,
Examples of the divalent hydrophobic group include an alkylene group having 4 or more carbon atoms, an alkenylene group having 4 or more carbon atoms, an arylene group having 6 or more carbon atoms, and a polyalkyleneoxy group having an alkylene group having 3 or more carbon atoms in the structure. It can be mentioned.

In the case where the gelling agent having an active hydrogen group is a hydrogel forming agent having an active hydrogen group, the ink film is heated to form a gel (that is, a hydrogel) incorporating water in the ink film. And the ink film effectively thickens.
When the gelling agent having an active hydrogen group is an amphiphilic gelling agent having an active hydrogen group, the ink film is heated to evaporate at least a part of the water from the ink film. And the hydrophobic groups of the amphiphilic gelling agents approach and aggregate. This allows the formation of hydrophobic segments (i.e., gels) and effectively thickens the ink film.
As described above, even when the gelling agent having an active hydrogen group is any of a hydrogelator having an active hydrogen group and an amphiphilic gelling agent having an active hydrogen group, the ink film is heated. The ink film can be effectively thickened.
Therefore, when the gelling agent having an active hydrogen group is a hydrogelator having an active hydrogen group and / or an amphiphilic gelling agent having an active hydrogen group, the effect of the ink of the present disclosure (image scratching) (Resistance and image definition) are more effective.

Hereinafter, each component which may be contained in the ink of the present disclosure will be described.

<Specific particle>
The specific particle is a urethane polymer, a urea polymer, or a (meth) acrylic polymer, and a polymer having a gelling group which is a reaction product of a gelling agent having an active hydrogen group and an isocyanate group (hereinafter also referred to as "specific polymer" At least one kind of

(Specific polymer)
The specific polymer is a urethane polymer, a urea polymer or a (meth) acrylic polymer. Each of these polymers has a strong structure. These strong structures also contribute to the effect of improving the scratch resistance of the image and the definition of the image.

In the present specification, a urethane polymer means a polymer containing a urethane group (except for the polymer corresponding to the (meth) acrylic polymer described later).
In the present specification, a urea polymer means a polymer containing a urea group (except for the above-mentioned urethane polymer or the polymer corresponding to the below-mentioned (meth) acrylic polymer).
In the present specification, a (meth) acrylic polymer is a homopolymer of one (meth) acrylate, a copolymer of two or more (meth) acrylates, or one or more (meth) acrylates By co-polymer with other monomers of species or more is meant.
The concept of urethane polymers also includes polymers containing both urethane groups and urea groups (so-called urethane urea polymers).
The term "(meth) acrylic polymer" also encompasses (meth) acrylic polymers containing at least one of a urethane group and a urea group.

The specific polymer is preferably a urethane polymer or a urea polymer from the viewpoint of more effectively exhibiting the effects (image scratch resistance and image definition) by the ink of the present disclosure.
When the specific polymer is a urethane polymer or a urea polymer, a pseudo crosslinked structure due to a hydrogen bond is likely to be formed between the urethane group or the urea group in the specific polymer and the gelling group. The formation of the pseudo crosslinked structure can more effectively thicken the ink film, and as a result, the scratch resistance of the image and the definition of the image can be further improved.

-Gelling group-
The specific polymer has at least one gelling group which is a reaction product of a specific gelling agent (i.e., a gelling agent having an active hydrogen group) and an isocyanate group.

The active hydrogen group in the specific gelling agent (ie, the gelling agent having an active hydrogen group) is preferably a hydroxy group, a primary amino group, or a secondary amino group from the viewpoint of the reactivity with the isocyanate group. Groups or primary amino groups are more preferred, and primary amino groups are particularly preferred.

There is no particular limitation on the valency of the gelling group (ie, the number of bonding sites on the gelling group).
That is, the gelling group may be a monovalent group or a divalent or higher group.
It is preferable that it is a monovalent group or a bivalent group from the viewpoint of the formation easiness of a gelling group.

Furthermore, from the viewpoint of further improving the scratch resistance of the image and the definition of the image, the gelling group is more preferably a monovalent group.
The reason is considered as follows.
When the gelling group is a monovalent group, the gelling group is a site having high thermal reactivity and high mobility, such as a specific polymer (for example, a specific linear polymer described later or a specific crosslinked polymer described later) It is not located in the backbone, but easily located at the end of the specific polymer. Therefore, when the gelling group is a monovalent group, the ink film can be more effectively thickened, and as a result, the scratch resistance of the image and the definition of the image are considered to be further improved.

From the viewpoint of further improving the scratch resistance of the image and the definition of the image, a further preferable embodiment of the specific polymer is that the gelling group is a monovalent group, and the specific polymer is a specific linear polymer described later; It is an aspect in which the gelling group which is a valence group is disposed at the end of the main chain of the specific linear polymer.
The reason for this is considered to be that the end of the main chain of the specific chain polymer is a site having higher thermal reactivity and higher mobility as compared to the end of the specific cross-linked polymer described later.

In the case where the gelling group is a divalent group and the specific polymer is a specific chain polymer described later, the gelling group is disposed in the main chain of the specific chain polymer.

The gelling group is preferably a group represented by the following formula (G).
The group represented by the formula (G) is a hydrogelator having an active hydrogen group or an amphiphilic gelling agent having an active hydrogen group as a specific gelling agent (that is, a gelling agent having an active hydrogen group) And an isocyanate group.

In formula (G), n ^G represents 1 or 2.
In terms of further improving the scratch resistance of the image and the definition of the image, n ^G is particularly preferably 1.
When n ^G is 1, it means that the group represented by the formula (G) is a monovalent group. Therefore, when n ^G in the formula (G) is 1, the scratch resistance of the image and the definition of the image are further improved due to the above-described presumed reason.

In formula (G), R ^U represents a urethane group, a urea group, a thiourethane group or a thiourea group. The R ^U is formed with the active hydrogen groups in the amphiphilic gelling agent having active hydrogen groups or active hydrogen groups in the hydrogel agent having an active hydrogen group, and isocyanate group, by reaction.

From the viewpoint of further improving the scratch resistance of the image and the definition of the image, as R ^U , a urethane group or a urea group is preferable, and a urea group is more preferable.
The following reasons can be considered as this reason.
As described above, the active hydrogen group is more preferably a hydroxy group or a primary amino group, particularly preferably a primary amino group, from the viewpoint of the reactivity with the isocyanate group.
The urethane group is a group formed by the reaction of a hydroxy group and an isocyanate group, and the urea group is a group formed by the reaction of a hydroxy group and a primary amino group.
Accordingly, when R ^U is a urethane group or a urea group (particularly preferably a urea group), the stability of the group represented by the formula (G) is enhanced, so the effect by the group represented by the formula (G) ( That is, the scratch resistance of the image and the improvement of the definition of the image are more effectively exhibited.

In Formula (G), L ^G represents a single bond or a divalent linking group.
As a divalent linking group, an alkylene group having 1 to 10 carbon atoms, a carbonyliminoalkylene group having 2 to 10 carbon atoms, an iminocarbonyl alkylene group having 2 to 10 carbon atoms, and a number average molecular weight of 1,000 or less (preferably 500 or less) And the like, and bivalent residues in which a hydroxy group is removed from both ends of the polyalkylene glycol which is
Here, a carbonylimino alkylene group means a divalent group in which a carbonyl group, an imino group and an alkylene group are linked in this order, and an iminocarbonyl alkylene group means an imino group, a carbonyl group and an alkylene group. It means a divalent group linked in this order.

In the formula (G), R ^G is a polysaccharide, a protein, an acrylic resin, a vinyl resin, or a hydrogelator which is a polyoxyalkylene compound represented by the formula (1) when n ^G is 1. It represents a residue from which one hydrogen atom has been removed, or a monovalent hydrophobic group.
In formula (G), when n ^G is 2, R ^G represents a residue obtained by removing two hydrogen atoms from the above hydrogelator, or represents a divalent hydrophobic group.
Here, the residue in which one hydrogen atom is removed from the hydrogelator and the residue in which two hydrogen atoms are removed from the hydrogelator are both partial structures in the hydrogelator having an active hydrogen group.
The monovalent hydrophobic group and the divalent hydrophobic group both have a partial structure in an amphiphilic gelling agent having an active hydrogen group (ie, a compound having an active hydrogen group and a hydrophobic group). It is.

Examples of polysaccharides (i.e., polysaccharides prior to removal of hydrogen atoms as residues) to form ^RG include agarose, agaropectin, amylose, amylopectin, gum arabic, sodium alginate, alginic acid Propylene glycol ester, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, curdlan, carrageenan, carboxymethyl cellulose, carboxymethyl starch, agar, xanthan gum, guar gum, quince seed, glucomannan, keratan sulfate, hydroxyethyl cellulose, hydroxypropyl cellulose, pectin, methyl starch Locust bean gum, dextrin, cyclodextrin and the like.
On the other hand, from the viewpoint of the easiness of formation of the group represented by the formula (G), as polysaccharides as the hydrogel forming agent, disaccharides to dodecasaccharides are preferable, trisaccharides to hexasaccharides are more preferable, Sugars to pentasaccharides are particularly preferred.

There is no particular limitation on the weight average molecular weight (Mw) of the polysaccharide.
The weight average molecular weight (Mw) of the polysaccharide is, for example, 300 to 1,000,000, preferably 400 to 100,000, more preferably 400 to 10,000, and particularly preferably 400 to 2,000.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) both mean values measured by gel permeation chromatography (GPC). However, for compounds whose accurate Mw can not be measured by GPC because of their small molecular weight, the molecular weight determined from the chemical structure of the compound is adopted as the Mw of the compound. The same applies to Mn.
In the present specification, gel permeation chromatography (GPC) measurement is carried out using HLC (registered trademark) -8020 GPC (Tosoh Corporation) as a measurement device, and TSKgel (registered trademark) Super Multipore HZ-H as a column. Three (4.6 mm ID × 15 cm, Tosoh Corp.) can be used, and THF (tetrahydrofuran) can be used as an eluent. In addition, as measurement conditions, the sample concentration is 0.45 mass%, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, and the measurement temperature is 40 ° C., using a differential refractive index (RI) detector .
The standard curve is the standard sample TSK standard, polystyrene of Tosoh Corp .: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A. It is made from eight samples of "-2500", "A-1000", and "n-propylbenzene".

When R ^G is a residue obtained by removing one or two hydrogen atoms from a polysaccharide as a hydrogelator, the group represented by the formula (G) is preferably a polysaccharide having a primary amino group Formed by
As a polysaccharide having a primary amino group, polysaccharides which are aminoethyl glycosides (for example, G0402, N0949 and S0946 in the following examples) or aminopropyl glycosides are preferable.
As an example of the group represented by the formula (G) formed using polysaccharides that are aminoethyl glycosides (for example, G0402, N0949 and S0946 in the examples described later), in the formula (G), n ^G is 1 and R ^U is a urea group formed by the reaction of an amino group and an isocyanate group, L ^G is an ethylene group (—CH ₂ CH ₂ — group), R ^G is a polysaccharide to hydrogen Examples include residues in which one atom has been removed.
As an example of the group represented by Formula (G) formed using the polysaccharide which is aminopropyl glycoside, in Formula (G), n ^G is 1, and R ^U is an amino group and an isocyanate group. An example in which L ^G is a propylene group (—CH ₂ CH ₂ CH ₂ — group) and R ^G is a residue obtained by removing one hydrogen atom from a polysaccharide, It can be mentioned.
The preferred range of the Mw of the polysaccharide having a primary amino group for forming a group represented by the formula (G) is the Mw of the polysaccharide described above (ie, the polysaccharide for forming ^RG ). It is the same as the preferred range.

There is no particular limitation on the protein as a hydrogel forming agent for forming ^RG (ie, the protein before being made into a residue except hydrogen atoms).
Proteins include gelatin.
The weight average molecular weight (Mw) of the protein is, for example, 1,000 to 100,000,000, preferably 5,000 to 10,000,000, and more preferably 10,000 to 100,000.

There is no particular limitation on the acrylic resin as a hydrogel forming agent for forming ^RG (that is, the acrylic resin before leaving hydrogen atom to be a residue).
The acrylic resin includes poly (N-isopropyl acrylamide).
The weight average molecular weight (Mw) of the acrylic resin is, for example, 1,000 to 500,000, preferably 5,000 to 100,000, and more preferably 10,000 to 50,000.

There is no particular limitation on the vinyl resin as a hydrogelating agent for forming ^RG (that is, the vinyl resin prior to leaving hydrogen atom to be a residue).
As a vinyl resin, polyvinyl alcohol is mentioned.
The weight average molecular weight (Mw) of the vinyl resin is, for example, 1,000 to 500,000, preferably 5,000 to 100,000, and more preferably 10,000 to 50,000.

A polyoxyalkylene compound represented by the formula (1) as a hydrogel forming agent for forming ^RG (i.e., a polyoxyalkylene compound represented by the formula (1) before being made into a residue excluding hydrogen atoms ) Is as follows.

In formula (1), n and m each independently represent an integer of 2 or more, p represents an integer of 0 or more, L represents an alkylene group having 3 or more carbon atoms, and R is a hydrogen atom , An alkyl group or an aryl group.

In the formula (1), the alkylene group represented by L may be a linear alkylene group or a branched alkylene group.
The carbon number of the alkylene group represented by L is 3 or more, preferably 3 to 6, more preferably 3 to 4, and particularly preferably 3.

In the formula (1), the alkyl group represented by R may be a linear alkyl group or a branched alkyl group.
The carbon number of the alkyl group represented by R is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 3.

In the formula (1), the carbon number of the aryl group represented by R is preferably 6 to 18, and more preferably 6 to 12.

In the formula (1), the alkyl group represented by R and the aryl group represented by R may each be substituted by a substituent.
Examples of the substituent include a halogen atom, an alkoxy group, and a carboxy group.

Specifically as the polyoxyalkylene compound represented by the formula (1),
Polyethylene glycol-polypropylene glycol block copolymer polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer,
Polypropylene glycol-polyethylene glycol-polypropylene glycol triblock copolymer,
Etc.

The number average molecular weight (Mn) of the polyoxyalkylene compound represented by the formula (1) is, for example, 500 to 500,000, preferably 1,000 to 100,000, and more preferably 2,000 to 30,000. And more preferably 2,000 to 20,000.

When R ^G is a residue obtained by removing one hydrogen atom from a polyoxyalkylene compound represented by the formula (1) as a hydrogel forming agent, the group represented by the formula (G) is preferably It is formed by the polyoxyalkylene compound represented by the formula (1A).

In formula (1A), n, m, p, L and R are respectively synonymous with n, m, p, L and R in formula (1), and preferred embodiments are also the same.
The polyoxyalkylene compound represented by the formula (1A) is a compound having one more oxyethylene unit relative to the polyoxyalkylene compound represented by the formula (1) (see “n + 1” in the formula (1A) ).

When the group represented by the formula (G) is formed by the polyoxyalkylene compound represented by the formula (1A), for example, a hydroxy group in the hydroxyethyl group of the terminal portion in the formula (1A) and an isocyanate group R ^U (urethane group) in the formula (G) is formed by the reaction of and the part of the ethyl group in the hydroxyethyl group becomes L ^G (ethylene group) in the formula (G), the formula (1A) The part except the said hydroxyethyl group from it becomes ^{RG in} Formula (G). This ^RG corresponds to a residue obtained by removing one hydrogen atom from the polyoxyalkylene compound represented by the formula (1). In this example, n ^G in equation (G) is 1.

The preferable range of Mn of the polyoxyalkylene compound represented by the formula (1A) for forming a group represented by the formula (G) is represented by the above-mentioned formula (1) for forming R ^G It is the same as the preferable range of Mn of the polyoxyalkylene compound.

A commercial item may be used as a polyoxyalkylene compound represented by Formula (1A).
Examples of commercially available products include Pluronic (registered trademark) F108 (Mn 14600, melting point 62 ° C.), P85 (Mn 4600, melting point 40 ° C.), and F87 (Mn 7700, melting point 49 ° C.) manufactured by BASF.

The hydrogel forming agent for forming ^RG in the formula (G) is a polysaccharide or a polyoxyalkylene compound represented by the formula (1) from the viewpoint of further improving the scratch resistance and the definition of the image of the image. It is preferable that it is a polysaccharide, more preferably it is a polysaccharide.

In formula (G), the monovalent hydrophobic group and the divalent hydrophobic group represented by ^RG are both amphiphilic gelling agents having an active hydrogen group (ie, active hydrogen group and hydrophobicity). And a partial structure in a compound having a sex group.

As the monovalent hydrophobic group represented by R ^G , as described above, an alkyl group having 4 or more carbon atoms, an alkenyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, and 3 or more carbon atoms in the structure Alkoxy alkyleneoxy group containing an alkylene group, alkoxypolyalkyleneoxy group containing an alkylene group having 3 or more carbon atoms in the structure, hydroxyalkyleneoxy group containing an alkylene group having 3 or more carbon atoms in the structure, carbon number in the structure Examples include hydroxypolyalkyleneoxy groups containing three or more alkylene groups.
As the divalent hydrophobic group represented by R ^G , as described above, an alkylene group having 4 or more carbon atoms, an alkenylene group having 4 or more carbon atoms, an arylene group having 6 or more carbon atoms, and 3 or more carbon atoms in the structure And a polyalkyleneoxy group containing an alkylene group of

The monovalent hydrophobic group represented by ^RG is preferably a linear alkyl group having 4 or more carbon atoms.
The carbon number of the linear alkyl group having 4 or more carbon atoms is preferably 7 or more, more preferably 10 or more, and more preferably 16 or more from the viewpoint of further improving the scratch resistance of the image and the definition of the image. Being particularly preferred.
The upper limit of the carbon number of the linear alkyl group having 4 or more carbon atoms is not particularly limited, but the upper limit is, for example, 30 and preferably 25.

The divalent hydrophobic group represented by R ^G is preferably a linear alkylene group having 4 or more carbon atoms.
The carbon number of the linear alkylene group having 4 or more carbon atoms is preferably 7 or more, more preferably 10 or more, and more preferably 16 or more, from the viewpoint of further improving the scratch resistance of the image and the definition of the image. Being particularly preferred.
The upper limit of the carbon number of the linear alkylene group having 4 or more carbon atoms is not particularly limited, but the upper limit is, for example, 30 and preferably 25.

The group represented by the formula (G) of the embodiment in which R ^G is a monovalent hydrophobic group or a divalent hydrophobic group is a reaction of an amphiphilic gelling agent having an active hydrogen group with an isocyanate group Formed by

The amphiphilic gelling agent having an active hydrogen group is preferably solid at room temperature (25 ° C.) from the viewpoint that the gelation function is more effectively exhibited in the ink film.
From this point of view, the melting point of the amphiphilic gelling agent having an active hydrogen group is preferably 40 ° C. or more, more preferably 60 ° C. or more, still more preferably 80 ° C. or more, particularly preferably 100 ° C. It is above.
The upper limit of the melting point of the amphiphilic gelling agent having an active hydrogen group is preferably 200 ° C. or less from the viewpoint of the production suitability of the amphiphilic gelling agent.

There is no particular limitation on the molecular weight of the amphiphilic gelling agent having an active hydrogen group.
The molecular weight of the amphiphilic gelling agent having an active hydrogen group is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1100 or less.
The molecular weight of the amphiphilic gelling agent is preferably 300 or more, more preferably 400 or more, and particularly preferably 500 or more.

As an amphiphilic gelling agent having an active hydrogen group, preferably
A linear alkylamine having 10 to 30 carbon atoms (more preferably 12 to 30 carbon atoms, still more preferably 15 to 30 carbon atoms, particularly preferably 15 to 15 carbon atoms),
A linear alkylene diamine having 10 to 30 carbon atoms (more preferably 12 to 30 carbon atoms, still more preferably 15 to 30 carbon atoms, and particularly preferably 15 to 15 carbon atoms),
A monoalkyl polyethylene glycol having a linear alkyl group having 10 to 30 carbon atoms (more preferably 12 to 30 carbon atoms, still more preferably 15 to 30 carbon atoms, and particularly preferably 15 to 15 carbon atoms), or
It has 10 to 30 carbon atoms (more preferably 12 to 30 carbon atoms, still more preferably 15 to 30 carbon atoms, particularly preferably 15 to 15 carbon atoms), and a hydroxyalkyl group, an amido group, an alkylene group, an amido group and a hydroxy group A compound in which an alkyl group is bonded in this order,
Particularly preferable are linear alkylamines having 10 to 30 carbon atoms (more preferably 12 to 30 carbon atoms, still more preferably 15 to 30 carbon atoms, and particularly preferably 15 to 15 carbon atoms).

Specific examples of the amphiphilic gelling agent having an active hydrogen group are eicosylamine (C ₂₀ H ₄₁ NH ₂ ), octadecylamine (C ₁₈ H ₃₇ NH ₂ ), hexadecylamine (C ₂₀ H ₄₁ NH ₂ ) in Examples described later. C ₁₆ H ₃₃ NH ₂ ), octylamine (C ₈ H ₁₇ NH ₂ ), 1,12-dodecyldiamine (H ₂ N (CH ₂ ) ₁₂ NH ₂ ), gel-01 to gel-06, monoalkyl polyethylene glycol , Etc.

As the amphiphilic gelling agent having an active hydrogen group, a compound having an active hydrogen group and a hydrophobic group may be selected and used from the gelling agents described in JP-A-2013-7039. .

The molecular weight of the gelling group (for example, a group represented by formula (G)) described above is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1100 or less.
The molecular weight of the gelling group is preferably 300 or more, more preferably 400 or more, and particularly preferably 500 or more.

-Preferred embodiment of specific polymer-
A preferred embodiment of the specific polymer is an embodiment (hereinafter also referred to as "embodiment A") which is a reaction product of a gelling agent having an active hydrogen group and a compound having an isocyanate group.
In the aspect A, the compound having an isocyanate group may be a raw material monomer for forming a polymer, or may be a polymer having an isocyanate group.
That is, in the embodiment A, the gelling agent may be incorporated into the structure of a specific polymer in the process of forming the specific polymer, or may be added to the polymer by polymer addition reaction to form a specific polymer It may be incorporated into the structure.

Examples of the compound having an isocyanate group in the embodiment A include, as raw material monomers having an isocyanate group, isocyanate compounds having two or more functional groups, (meth) acrylate having at least one isocyanate group, and the like.
As a compound having an isocyanate group in aspect A, as a polymer having an isocyanate group, a urethane polymer having at least one isocyanate group, a urea polymer having at least one isocyanate group, a (meth) acrylic polymer having at least one isocyanate group , Etc.

The specific polymer may be a linear polymer having no crosslinked structure (hereinafter also referred to as “specific linear polymer”), or a polymer having a crosslinked structure (for example, a three-dimensional crosslinked structure) (hereinafter, “specific It may also be referred to as "crosslinked polymer".
The specific chain polymer may contain cyclic structures such as aliphatic rings, aromatic rings, and heterocyclic rings in the main chain.
For the three-dimensional crosslinked structure that the specific crosslinked polymer may have, reference may be made to the three-dimensional crosslinked structure described in WO 2016/052052.

-Specific linear polymer-
Specific chain polymers are
A gel having an active hydrogen group, and a reaction product A1 of a reaction product of at least one selected from the group consisting of bifunctional isocyanate compounds and at least one compound selected from the group consisting of water and a compound having two active hydrogen groups A reaction product A2 of an agent, or
Reaction product B1 of a reaction product of at least one compound selected from the group consisting of bifunctional isocyanate compounds with at least one compound selected from the group consisting of water and a compound having two active hydrogen groups, and other compounds It is preferable that it is a reaction product B2 of a gelling agent having a group.

As a compound which has two active hydrogen groups, a diol compound, a diamine compound, and a dithiol compound are mentioned.
For example, a urethane group is formed by the reaction of a difunctional isocyanate compound and a diol compound.
Further, a urea group is formed by the reaction of a bifunctional isocyanate compound and a diamine compound.
Moreover, a urea group is formed by the reaction of a bifunctional isocyanate compound and water.

Moreover, as the above other compounds,
Among the compounds for introducing a polymerizable group described later, a compound containing only one active hydrogen group,
Among the isocyanate compounds into which a polymerizable group described later is introduced, a compound containing only one isocyanate group,
Among the compounds for introducing a hydrophilic group described later, a compound containing only one active hydrogen group,
Among the isocyanate compounds into which a hydrophilic group described later is introduced, a compound containing only one isocyanate group,
Etc.

The following compounds (1-1) to (1-20) may be mentioned as the bifunctional isocyanate compound for forming the specific chain polymer.

Examples of the compound having two active hydrogen groups for forming a specific chain polymer include the following compounds (2-1) to (2-24).

Moreover, as a compound which has two active hydrogen groups for forming a specific chain | strand-shaped polymer, the compound which contains two active hydrogen groups among the compounds for polymeric group introduction | transduction mentioned later, for hydrophilic group introduction mentioned later Among the compounds, compounds containing two active hydrogen groups, and the like can also be mentioned.

-Specific cross-linked polymer-
The specific crosslinked polymer is
A reaction product C1 of at least one selected from the group consisting of trifunctional or higher functional isocyanate compounds and at least one selected from the group consisting of water and a compound having two or more active hydrogen groups, and an active hydrogen group A reaction product C2 of a gelling agent having
A reaction product D1 of at least one compound selected from the group consisting of trifunctional or higher isocyanate compounds and a compound having two or more active hydrogen groups and at least one compound selected from the group consisting of water with other compounds It is preferable that it is a reaction product D2 with a gelling agent having an active hydrogen group.

As the above other compounds,
Among the compounds for introducing a polymerizable group described later, a compound containing only one active hydrogen group,
Among the isocyanate compounds into which a polymerizable group described later is introduced, a compound containing only one isocyanate group,
Among the compounds for introducing a hydrophilic group described later, a compound containing only one active hydrogen group,
Among the isocyanate compounds into which a hydrophilic group described later is introduced, a compound containing only one isocyanate group,
Etc.

When the specific particle contains a specific crosslinked polymer, the specific particle preferably contains a microcapsule (hereinafter, “MC”) including a shell made of the specific crosslinked polymer and a core.

Examples of compounds having two or more active hydrogen groups for forming a specific crosslinked polymer include diol compounds and diamines, as well as compounds having two active hydrogen groups for forming the specific linear polymer described above. Compounds and dithiol compounds are included.
Moreover, as a compound which has a 2 or more active hydrogen group for forming a specific crosslinked polymer, the trifunctional or more than trifunctional polyol compound, the trifunctional or more than trifunctional polyamine compound, and the trifunctional or more polythiol compound are also mentioned.

The trifunctional or higher functional isocyanate compound for forming the specific crosslinked polymer is a compound having at least one selected from the group consisting of bifunctional isocyanate compounds and three or more active hydrogen groups (for example, trifunctional or higher functional compounds) It is preferable that it is a reaction product with at least 1 sort (s) selected from the group which consists of a polyol compound, a trifunctional or more than trifunctional polyamine compound, and a trifunctional or more than trifunctional polythiol compound).
The number of moles (number of molecules) of the bifunctional isocyanate compound to be reacted with the compound having three or more active hydrogen groups is the number of moles of active hydrogen groups in the compound having three or more active hydrogen groups (equivalent weight of active hydrogen groups The number is preferably 0.6 times or more, more preferably 0.6 times to 5 times, still more preferably 0.6 times to 3 times, and still more preferably 0.8 times to 2 times.

As a bifunctional isocyanate compound for forming the trifunctional or more than trifunctional isocyanate compound, the thing similar to the bifunctional isocyanate compound for forming the specific chain | strand-shaped polymer mentioned above is mentioned.

Examples of the compound having three or more active hydrogen groups for forming a trifunctional or higher functional isocyanate compound include compounds having structures represented by the following (H-1) to (H-13). In the following structure, n represents an integer selected from 1 to 100.

Examples of trifunctional or higher functional isocyanate compounds used to form the specific crosslinked polymer include adduct type trifunctional or higher isocyanate compounds, isocyanurate type trifunctional or higher isocyanate compounds, biuret type trifunctional or higher isocyanate compounds, and the like. It can be mentioned.
As commercial products of the adduct type trifunctional or higher isocyanate compound, Takenate (registered trademark) D-102, D-103, D-103H, D-103M2, P49-75S, D-110N, D-120N, D- 140N, D-160N (above, Mitsui Chemical Co., Ltd.), Desmodur (registered trademark) L75, UL57SP (Sumikawa Bayer Urethane Co., Ltd.), Coronate (registered trademark) HL, HX, L (Nippon Urethane Polymer (Japan Urethane Polymer Co., Ltd. ), P301-75E (Asahi Kasei Corporation) and the like.
As commercial products of isocyanurate type trifunctional or higher isocyanate compounds, Takenate (registered trademark) D-127N, D-170N, D-170HN, D-172N, D-177N (all, Mitsui Chemicals, Inc.), Sumidur N3300, Desmodur (registered trademark) N3600, N3900, Z4470BA (above, Sumika Bayer Urethane Co., Ltd.), Coronate (registered trademark) HX, HK (above, Nippon Urethane Polymer Co., Ltd.), Duranate (registered trademark) TPA-100, TKA-100, TSA-100, TSS-100, TLA-100, TSE-100 (all, Asahi Kasei Corporation) and the like.
As commercial products of biuret type trifunctional or higher isocyanate compounds, Takenate (registered trademark) D-165N, NP1100 (Mitsui Chemical Co., Ltd.), Desmodur (registered trademark) N3200 (Suzuki Bayer Urethane Co., Ltd.) And Duranate (registered trademark) 24A-100 (Asahi Kasei Corporation).

In addition, when the specific particle includes an MC (that is, a microcapsule) containing a shell made of a specific crosslinked polymer and a core, the specific particle is hydrophilic as a dispersant for MC, among the specific linear polymers described above. You may contain the specific linear polymer of the aspect which has group. In the ink in this aspect, at least a part of the periphery of the shell of MC can be in a state of being coated with a specific linear polymer as a dispersant. In this aspect, the interaction between the urethane group and / or the urea group possessed by the shell of MC and the urethane group and / or the urea group possessed by the dispersant (specific chain polymer) and the hydrophilic group of the dispersant The dispersing action is combined to further improve the dispersion stability of the specific particles.
In this embodiment, the ratio of the amount of dispersant to the total solid content of MC (hereinafter also referred to as mass ratio [also referred to as dispersant / MC solid content]) is preferably 0.005 to 1.000, and 0.1. More preferably, it is from 05 to 0.7.
When the mass ratio [dispersant / MC solid content] is 0.005 or more, the dispersion stability of the specific particles is further improved.
When the mass ratio [dispersant / MC solid content] is 1.000 or less, the hardness of the image is further improved.

-Preferred weight average molecular weight (Mw) of specific polymer-
The weight average molecular weight (Mw) of the specific polymer is preferably 5000 or more, more preferably 7,000 or more, and 8000 or more from the viewpoint of the dispersion stability of the ink (that is, the dispersion stability of the specific particles). It is further preferred that
There is no particular limitation on the upper limit of Mw of the specific polymer. As an upper limit of Mw of a specific polymer, 150000, 100000, 70000, 50000 are mentioned, for example.

The content of the specific polymer is preferably 10% by mass or more, and more preferably 20% by mass or more based on the total solid content of the specific particles.
When the content of the specific polymer is 10% by mass or more based on the total solid content of the specific particles, the dispersion stability of the ink (that is, the dispersion stability of the specific particles) is further improved.
The content of the specific polymer may be 100% by mass with respect to the total solid content of the specific particles, but 80% by mass or less is preferable, 70% by mass or less is more preferable, and 50% by mass or less Being particularly preferred.

-Polymerizable group-
The specific polymer preferably has at least one kind of polymerizable group.
When the specific polymer has a polymerizable group, after thickening the ink film by the action of the gelling group, the thickened ink film can be cured by the action of the polymerizable group.
This further improves the scratch resistance of the image.

As a polymeric group, a photopolymerizable group or a thermally polymerizable group is preferable.
The photopolymerizable group is preferably a radical polymerizable group, more preferably a group containing an ethylenic double bond, and still more preferably a (meth) acryloyl group, an allyl group, a styryl group or a vinyl group. As the radically polymerizable group, a (meth) acryloyl group is particularly preferable from the viewpoint of radical polymerization reactivity and the hardness of the formed film.
As the thermally polymerizable group, an epoxy group, an oxetanyl group, an aziridinyl group, an azetidinyl group, a ketone group, an aldehyde group or a blocked isocyanate group is preferable.
The specific polymer may contain only one type of polymerizable group, or may contain two or more types.
The specific polymer having a polymerizable group can be confirmed, for example, by Fourier transform infrared spectroscopy (FT-IR) analysis.

-Compound for introducing polymerizable group-
When the specific polymer has a polymerizable group, the introduction of the polymerizable group into the specific polymer can be performed using a compound for introducing a polymerizable group.
As the compound for introducing a polymerizable group, a compound having a polymerizable group and an active hydrogen group can be used.
As the compound for introducing a polymerizable group, it is preferable to use a compound having one or more polymerizable groups and two or more active hydrogen groups.

The method for introducing the polymerizable group into the specific polymer is not particularly limited, but when synthesizing the specific polymer, at least one selected from the group consisting of a bifunctional isocyanate compound, water, a diol compound, and a diamine compound And at least one selected from the group consisting of dithiol compounds, at least one compound for introducing a polymerizable group, and (when necessary, at least one compound for introducing a hydrophilic group), the method is particularly preferred. preferable.
The polymerizable group-introducing monomer may be used alone or in combination of two or more.

As the compound for introducing a polymerizable group, for example, the compounds described in paragraphs 0075 to 0089 of WO 2016/052053 can also be used.

As the compound for introducing a polymerizable group, a compound represented by the following formula (ma) is preferable.
L ¹ Lc _m Z _n (ma)

In formula (ma), L ¹ represents a m + n valent linking group, m and n each independently represent an integer selected from 1 to 100, and L c represents a monovalent ethylenically unsaturated group, Z represents an active hydrogen group.
L ¹ is a divalent or higher aliphatic group, a divalent or higher aromatic group, a divalent or higher heterocyclic group, -O-, -S-, -NH-, -N <, -CO-, -SO It is preferable that-, -SO ₂ -or a combination thereof.
m and n each independently are preferably 1 to 50, more preferably 2 to 20, still more preferably 3 to 10, and particularly preferably 3 to 5.
Examples of the monovalent ethylenically unsaturated group represented by Lc include an allyl group, a vinyl group, an acryloyl group and a methacryloyl group.
The active hydrogen group represented by Z is more preferably a hydroxy group or a primary amino group, and still more preferably a hydroxy group.

Hereinafter, although the example of a compound for polymeric group introduction is shown, the compound for polymeric group introduction is not limited to the following examples. Here, n in the compounds (a-3) and (a-14) represents, for example, an integer selected from 1 to 90.

-Isocyanate compound introduced with a polymerizable group-
When the specific polymer has a polymerizable group, the introduction of the polymerizable group into the specific polymer can also be carried out using an isocyanate compound having a polymerizable group introduced.
As an isocyanate compound which introduce | transduced the polymeric group,
Reaction product of at least one of the above-mentioned compounds for introducing a polymerizable group and at least one of a bifunctional isocyanate compound;
Reaction product of at least one of the above-mentioned compounds for introducing a polymerizable group and at least one of an isocyanate compound having three or more functional groups;
From the group consisting of at least one of the above-mentioned compounds for introducing a polymerizable group, at least one of a bifunctional isocyanate compound, a trifunctional or higher polyol compound, a trifunctional or higher polyamine compound, and a trifunctional or higher polythiol compound Reaction products of at least one selected;
Etc.

-Hydrophilic group-
The specific polymer may have at least one hydrophilic group.
When the specific polymer has a hydrophilic group, the dispersion stability (for example, storage stability, ejection stability, etc.) of the ink is improved.
As a hydrophilic group, an anionic group or a nonionic group is preferable, and an anionic group is preferable from the point which is excellent in the effect of a dispersion stability improvement.
For example, when the anionic group and the nonionic group of the same molecular weight are compared, the anionic group is more excellent in the effect of improving the dispersion stability. That is, an anionic group (particularly preferably at least one member selected from the group consisting of a carboxy group and a salt of a carboxy group) can sufficiently exhibit the effect of improving the dispersion stability even when the molecular weight is small. .

The nonionic group includes a group having a polyether structure, and is preferably a monovalent group containing a polyalkyleneoxy group.

The anionic group may be an unneutralized anionic group or a neutralized anionic group.
As an anionic group which is not neutralized, a carboxy group, a sulfo group, a sulfuric acid group, a phosphonic acid group, a phosphoric acid group etc. are mentioned.
Examples of the neutralized anionic group include salts of carboxy group, salts of sulfo group, salts of sulfuric acid group, salts of phosphonic acid group, salts of phosphoric acid group, and the like.

In the present specification, "a carboxy group is neutralized" indicates that a carboxy group as an anionic group is in the form of a "salt" (eg, "-COONa"). The same applies to a sulfo group, a sulfate group, a phosphonate group and a phosphate group as an anionic group.
Neutralization can be performed, for example, using an alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide etc.), an organic amine (eg, triethylamine etc.).

From the viewpoint of dispersion stability, as the anionic group that the specific polymer may have, a carboxy group, a salt of a carboxy group, a sulfo group, a salt of a sulfo group, a sulfate group, a salt of a sulfate group, a phosphonic acid group, a phosphonic acid group And at least one selected from the group consisting of salts of phosphoric acid groups and salts of phosphoric acid groups, and more preferably at least one selected from the group consisting of carboxy groups and salts of carboxy groups.
As the “salt” in the salts of carboxy group, salts of sulfo group, salts of sulfuric acid group, salts of phosphonic acid group and salts of phosphoric acid group described above, alkali metal salts or organic amine salts are preferable, and alkali metal salts Is more preferred.
As the alkali metal in the alkali metal salt, K or Na is preferable.

When the specific polymer has a neutralized anionic group, the degree of neutralization of the anionic group (eg, carboxy group) of the specific polymer is preferably 50% to 100%.
In the present specification, the "degree of neutralization of anionic group" means the number of moles of neutralized anionic group and the number of moles of non-neutralized anionic group in the entire anionic group of the specific polymer. Ratio of the number of moles of neutralized anionic groups to the total of [number of moles of neutralized acid groups / (number of moles of neutralized acid groups + number of moles of non-neutralized acid groups)] means.
When the degree of neutralization of the anionic group is 50% or more, the dispersion stability of the specific particle is further improved.
The degree of neutralization of the anionic group is preferably 50% to 95%, more preferably 80% to 95%, and still more preferably 90% to 95%.
The neutralized anionic group (ie, an anionic group in the form of a salt) exhibits basicity. When the degree of neutralization of the anionic group is 95% or less, the hydrolysis of the urethane group and / or the urea group which the specific polymer may have can be further suppressed.
The degree of neutralization can be determined by neutralization titration.

Furthermore, in the case where the specific polymer contains an anionic group (for example, at least one selected from the group consisting of a carboxy group and a salt of a carboxy group) as a hydrophilic group, the number of millimoles of anionic group in 1 g of the specific polymer ( For example, in the case where the total millimole number of the carboxy group and the salt of the carboxy group is the acid value of the specific polymer, the acid value of the specific polymer is 0.10 mmol / g to 2.10 from the viewpoint of the dispersion stability of the specific particles. It is preferably 00 mmol / g, more preferably 0.30 mmol / g to 1.50 mmol / g.

-Compound for introducing hydrophilic group-
When the specific polymer in the specific particle has a hydrophilic group, the introduction of the hydrophilic group into the specific polymer can be performed using a compound for introducing a hydrophilic group.
As a compound for hydrophilic group introduction, a compound having a hydrophilic group and an active hydrogen group can be used.
It is preferable to use a compound having one or more hydrophilic groups and two or more active hydrogen groups as the hydrophilic group-introducing compound.

Among the compounds for introducing a hydrophilic group, as compounds for introducing an anionic group, α-amino acids (specifically, lysine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, Amino acids such as leucine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine and valine) can be mentioned.
As the compound for introducing an anionic group, the following specific examples can be mentioned besides the above-mentioned α-amino acid.

The compound for introducing an anionic group may be used by neutralizing at least a part of the anionic group, using an inorganic base such as sodium hydroxide or potassium hydroxide; an organic base such as triethylamine; or the like.

Among the hydrophilic group-introducing compounds, as the nonionic group-introducing compound, compounds having a polyether structure are preferable, and compounds having a polyoxyalkylene group are more preferable.

-Isocyanate compound introduced hydrophilic group-
When the specific polymer in the specific particle has a hydrophilic group, the introduction of the hydrophilic group into the specific polymer can also be performed using an isocyanate compound having a hydrophilic group introduced.
As the isocyanate compound which introduced the hydrophilic group,
Reaction product of at least one of the hydrophilic group-introducing compounds described above and at least one of the bifunctional isocyanate compounds;
Reaction product of at least one of the hydrophilic group-introducing compounds described above and at least one of trifunctional or higher functional isocyanate compounds;
From the group consisting of at least one of the hydrophilic group-introducing compounds described above, at least one of the bifunctional isocyanate compounds, a trifunctional or higher polyol compound, a trifunctional or higher polyamine compound, and a trifunctional or higher polythiol compound Reaction products of at least one selected;
Etc.

Specific examples of the isocyanate compound having a hydrophilic group introduced include adducts of trimethylolpropane (TMP), m-xylylene diisocyanate (XDI) and polyethylene glycol monomethyl ether (EO) (for example, Mitsui Chemicals, Inc. Takenate (registered trademark) D-116N).

(Polymerizable monomer)
The specific particles preferably contain a polymerizable monomer.
When the specific particles contain a polymerizable monomer, after thickening the ink film by the action of the gelling group, the thickened ink film can be cured by the action of the polymerizable monomer.
This further improves the scratch resistance of the image.
When the specific particle contains a polymerizable monomer, the polymerizable monomer contained in the specific particle may be only one type, or two or more types.

As the polymerizable monomer contained in the specific particles, the compounds described in paragraphs 0097 to 0105 of WO 2016/052053 may be used.

As the polymerizable monomer contained in the specific particles, a photopolymerizable monomer or a thermally polymerizable monomer is preferable.
The photopolymerizable monomer has the property of polymerizing upon irradiation with light (ie, active energy ray).
The thermally polymerizable monomer has a property of polymerizing by heating or irradiation of infrared radiation.
As the photopolymerizable monomer, a radically polymerizable monomer having a radically polymerizable ethylenic double bond is preferable.

In the present specification, the ink in which the specific particle contains at least one of the photopolymerizable monomer and the specific polymer has a photopolymerizable group is referred to as “photocurable ink”. The ink of an aspect satisfying at least one of the specific particles containing a thermally polymerizable monomer and the specific polymer having a thermally polymerizable group may be referred to as a "thermosetting ink".
When the ink of the present disclosure is a photocurable ink, curing of the ink film formed by the ink of the present disclosure can be performed by applying light to the ink film (curing process described later) A) When the ink of the present disclosure is a thermosetting ink, the ink film can be heated or subjected to infrared irradiation (see heating step or curing step B described later).

A preferred embodiment of the photocurable ink is an embodiment in which the specific particles contain a photopolymerizable monomer and the specific polymer has a photopolymerizable group.
As a result, the hardenability of the image by irradiation with active energy rays is further improved, and the scratch resistance of the image is further improved.

When the specific particle contains a photopolymerizable monomer as a polymerizable monomer, the specific particle preferably further contains a photopolymerization initiator described later.
When the specific particles contain a thermally polymerizable monomer as a polymerizable monomer, the specific particles may further contain a photothermal conversion agent, a thermal curing accelerator, or a photothermal conversion agent and a thermal curing accelerator described later.

The content of the polymerizable monomer contained in the specific particles (total amount in the case of containing two or more types) is 10 mass with respect to the total solid content of the specific particles from the viewpoint of improving the curing sensitivity of the film and the hardness of the film. % To 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is more preferable.

In the present specification, the total solid content of a specific particle means the total amount of the specific particle when the specific particle does not contain a solvent, and when the specific particle contains a solvent, the solvent is removed from the specific particle. It means the total amount.

The molecular weight of the polymerizable monomer is preferably 100 to 4000, more preferably 100 to 2000, still more preferably 100 to 1000, still more preferably 100 to 900, and still more preferably 100 to 800. And particularly preferably 150 to 750.

-Photopolymerizable monomer-
As the photopolymerizable monomer, a polymerizable monomer having a radically polymerizable ethylenic unsaturated bond (ie, a radically polymerizable monomer) and a polymerizable monomer having a cationically polymerizable cationically polymerizable group (ie, a cationically polymerizable monomer Can be selected from

Examples of radically polymerizable monomers include acrylate compounds, methacrylate compounds, styrenic compounds, vinyl naphthalene compounds, N-vinyl heterocyclic compounds, unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.
The radically polymerizable monomer is preferably a compound having an ethylenically unsaturated group.
When the specific particle contains a radically polymerizable monomer, the specific particle may contain only one type of radically polymerizable monomer, or may contain two or more types.

As an acrylate compound, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, tridecyl acrylate, 2-phenoxyethyl acrylate (PEA), bis (4-acryloxypoly) Ethoxyphenyl) propane, oligoester acrylate, epoxy acrylate, isobornyl acrylate (IBOA), dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, dicyclopentanyl acrylate, cyclic trimethylolpropane formal acrylate, 2- (2 -Ethoxyethoxy) ethyl acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate , Octyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, isoamyl acrylate, stearyl acrylate, isoamyl still acrylate, isostearyl acrylate, 2-ethylhexyl di- Glycol acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethyl hydrophthalic acid, ethoxydiethylene glycol acrylate, methoxy diethylene glycol acrylate, methoxy polyethylene glycol acrylate, methoxy propylene glycol acrylate, 2-hydroxy-3-phenoxy propyl acrylate, vinyl ether acrylate, 2 - Cryloyl oxyethyl succinic acid, 2-acryloyl oxy phthalic acid, 2-acryloxy ethyl 2-hydroxyethyl phthalic acid, lactone modified acrylate, acryloyl morpholine, acrylamide, substituted acrylamide (for example, N-methylol acrylamide, and diacetone acrylamide) Monofunctional acrylate compounds such as

Polyethylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate (HDDA), 1, 9 -Nonanediol diacrylate (NDDA), 1,10-decanediol diacrylate (DDDA), 3-methylpentadiol diacrylate (3MPDDA), neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A ethylene oxide ( EO) adduct diacrylate, bisphenol A propylene oxide (PO) adduct diacrylate, ethoxylated bisphenol A diacrylate, hydrogen Roxypine pentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, alkoxylated dimethylol tricyclodecane diacrylate, polytetramethylene glycol diacrylate, alkoxylated cyclohexanone dimethanol diacrylate, alkoxylated hexanediol diacrylate, dioxane glycol Diacrylate, cyclohexanone dimethanol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate (TPGDA), neopentyl glycol propylene oxide adduct diacrylate, etc. Two-functional Aclay Compound;

Trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta Acrylate, dipentaerythritol hexaacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, caprolactone modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxytetraacrylate, glycerin propoxy triacrylate, ethoxylated Zipe Data hexaacrylate, caprolactam modified dipentaerythritol hexaacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, such as trifunctional or more acrylate compounds such as propoxylated trimethylol propane triacrylate.

As methacrylate compounds, methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, methoxypolyethylene glycol methacrylate, methoxytriethylene glycol methacrylate, hydroxyethyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate and the like Monofunctional methacrylate compounds;

Examples include difunctional methacrylate compounds such as polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane and tetraethylene glycol dimethacrylate.

Examples of the styrene compound include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene and the like.

Examples of the vinyl naphthalene compound include 1-vinyl naphthalene, methyl-1-vinyl naphthalene, β-methyl-1-vinyl naphthalene, 4-methyl-1-vinyl naphthalene, 4-methoxy-1-vinyl naphthalene and the like.

Examples of N-vinyl heterocyclic compounds include N-vinylcarbazole, N-vinylpyrrolidone, N-vinylethylacetamide, N-vinylpyrrole, N-binyphenothiazine, N-vinylacetanilide, N-vinylethylacetamide, N-vinylsuccinic acid Imide, N-vinyl phthalimide, N-vinyl caprolactam, N-vinyl imidazole and the like can be mentioned.

Other radically polymerizable monomers include N-vinylamides such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, N-vinylformamide and the like.

Among these radically polymerizable monomers, as a radically polymerizable monomer having two or less functional groups, 1,6-hexanediol diacrylate (HDDA), 1,9-nonanediol diacrylate (NDDA), 1,10-decanediol Diacrylate (DDDA), 3-methylpentadiol diacrylate (3MPDDA), neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol Diacrylate (TPGDA), cyclohexanone dimethanol diacrylate, alkoxylated hexanediol diacrylate, polyethylene glycol diacrelay And at least one is preferably selected from polypropylene glycol diacrylate.
Moreover, as a radically polymerizable monomer having 3 or more functions, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ethoxylated Trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, caprolactone modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, pentaerythritol ethoxy tetraacrylate, glycerin propoxy triacrylate, ethoxylated dipentaerythritol hexaacrylate, caprolactam modified dipentaeri Li hexaacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated at least one selected from trimethylolpropane triacrylate are preferred.

The specific particles may contain a combination of a difunctional or less radically polymerizable monomer and a trifunctional or more radically polymerizable monomer. In this case, the difunctional or less radically polymerizable monomer contributes to the adhesion between the image and the substrate, and the trifunctional or more radically polymerizable monomer contributes to the improvement of the image hardness.
As a combination of a difunctional or less radically polymerizable monomer and a trifunctional or more radically polymerizable monomer, a combination of a difunctional acrylate compound and a trifunctional acrylate compound, a difunctional acrylate compound and a pentafunctional acrylate compound And combinations of monofunctional acrylate compounds and tetrafunctional acrylate compounds.

From the viewpoint of further improving the adhesion between the image and the substrate, at least one of the radically polymerizable monomers that may be contained in the specific particles is also a radically polymerizable monomer having a cyclic structure (hereinafter, "cyclic radically polymerizable monomer") Is preferred.
As a cyclic radically polymerizable monomer, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, dicyclopentanyl acrylate, ethoxylated isocyanuric acid triacrylate, ε -Caprolactone modified tris- (2-acryloxyethyl) isocyanurate and the like.
In addition, bifunctional or higher cyclic radical polymerizable monomers described below are also included.

From the viewpoint of further improving the adhesion between the image and the substrate, at least one of the radically polymerizable monomers that may be contained in the specific particles has one or more cyclic structures and two or more (meta It is preferable that it is a polymerizable monomer containing an acryloyl group (hereinafter, also referred to as “a cyclic radical polymerizable monomer having two or more functional groups”).
As a bifunctional or higher cyclic radically polymerizable monomer,
Tricyclodecane dimethanol di (meth) acrylate,
Bisphenol A ethylene oxide (EO) adduct di (meth) acrylate,
Bisphenol A propylene oxide (PO) adduct di (meth) acrylate,
Ethoxylated bisphenol A di (meth) acrylate,
Alkoxylated dimethylol tricyclodecane di (meth) acrylate,
Alkoxylated cyclohexanone dimethanol di (meth) acrylate,
Examples thereof include cyclohexanone dimethanol di (meth) acrylate and the like.

When the specific particles contain a radically polymerizable monomer, the proportion of the bifunctional or higher cyclic radically polymerizable monomer in the entire polymerizable monomer is preferably 10% by mass to 100% by mass, and more preferably 30% by mass to 100% by mass. Preferably, 40% by mass to 100% by mass is particularly preferable.

In addition to the above-mentioned radically polymerizable monomers, Y. Yamashita, 3rd. Ed., "Crosslinking Agent Handbook", (1981 Taiseisha); Kato Seikohen, "UV · EB Curing Handbook (raw materials)" (1985) "Polymer publication"; Rad Tech Research Group, "Application and market of UV / EB curing technology", page 79, (1989, CMC); Eiichiro Takiyama, "Polyester resin handbook", (1988, Nikkan Kogyo Co., Ltd.) Commercial products described in Shimbunsha et al., And radically polymerizable and crosslinkable monomers known in the art can be used.

Examples of cationically polymerizable monomers include epoxy compounds, vinyl ether compounds, and oxetane compounds.
As a cationically polymerizable monomer, a compound having at least one olefin, thioether, acetal, thioxane, thietane, aziridine, N heterocycle, O heterocycle, S heterocycle, P heterocycle, aldehyde, lactam, or cyclic ester group preferable.

As cationically polymerizable monomers, see "Advances in Polymer Science" by J. V. Crivello et al., 62, pages 1 to 47 (1984), "Handbook of Epoxy Resins" by Lee et al., McGraw Hill Book Company, New York (1967). And P. F. Bruins et al., “Epoxy Resin Technology”, (1968) may be used.

Also, as the photopolymerizable monomer, JP-A-77-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011, and the like can be used. The photocurable polymerizable monomers used in the photopolymerizable compositions described in the respective publications such as Table 2004-514014 are known, and these may also be applied as polymerizable monomers which can be contained in specific particles. it can.

As a photopolymerizable monomer, you may use the commercial item marketed.
Examples of commercial products of the photopolymerizable monomer include AH-600 (bifunctional), AT-600 (bifunctional), UA-306H (six functional), UA-306T (six functional), UA-306I (six functional) ), UA-510H (10 functional), UF-8001G (bifunctional), DAUA-167 (bifunctional), light acrylate NPA (bifunctional), light acrylate 3EG-A (bifunctional) (all, Kyoeisha Chemical (stock) ), SR339A (PEA, monofunctional), SR506 (IBOA, monofunctional), CD262 (bifunctional), SR238 (HDDA, bifunctional), SR341 (3MPDDA, bifunctional), SR508 (bifunctional), SR306H (2 Functional), CD 560 (bifunctional), SR833S (bifunctional), SR444 (trifunctional), SR454 (trifunctional), SR492 (trifunctional), SR 99 (trifunctional), CD501 (trifunctional), SR502 (trifunctional), SR9020 (trifunctional), CD9021 (trifunctional), SR9035 (trifunctional), SR494 (tetrafunctional), SR399E (trifunctional) (above, Sartmar, A-NOD-N (NDDA, bifunctional), A-DOD-N (DDDA, bifunctional), A-200 (bifunctional), APG-400 (bifunctional), A-BPE-10 (bifunctional) Bifunctional), A-BPE-20 (bifunctional), A-9300 (trifunctional), A-9300-1CL (trifunctional), A-TMPT (trifunctional), A-TMM-3L (trifunctional), A-TMMT (4 functions), AD-TMP (4 functions) (above, Shin-Nakamura Chemical Co., Ltd.), UV-7510 B (3 functions) (Japan Synthetic Chemical Co., Ltd.), KAYARAD DPCA-30 (6 functions) ), KAYARA DPEA-12 (6 functional) (Nippon Kayaku Co.) and the like.
In addition, as polymerizable monomers, NPGPODA (neopentyl glycol propylene oxide adduct diacrylate), SR 531, SR 285, SR 256 (above, Sartomer), A-DHP (dipentaerythritol hexaacrylate, Shin-Nakamura Chemical Co., Ltd.) Commercial products such as Alonics (registered trademark) M-156 (Toagosei Co., Ltd.), V-CAP (BASF Corporation), and Viscote # 192 (Osaka Organic Chemical Industry Co., Ltd.) can be suitably used.
Among these commercially available products, SR506, SR833S, A-9300, or A-9300-CL, which is a photopolymerizable monomer having a cyclic structure, is particularly preferable, and SR833S is particularly preferable.

-Thermally polymerizable monomer-
The thermally polymerizable monomers can be selected from the group of polymerizable monomers that can be polymerized by heating or irradiation with infrared radiation. As a thermally polymerizable monomer, an epoxy compound, an oxetane compound, an aziridine compound, an azetidine compound, a ketone compound, an aldehyde compound, a block isocyanate compound etc. are mentioned, for example.

As an epoxy compound, 1,4-butanediol diglycidyl ether, 3- (bis (glycidyloxymethyl) methoxy) -1,2-propanediol, limonene oxide, 2-biphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl -3 ', 4'-Epoxycyclohexanecarboxylate, epoxide derived from epichlorohydrin-bisphenol S, epoxidized styrene, epoxide derived from epichlorohydrin-bisphenol F, epoxide derived from epichlorohydrin-bisphenol A, epoxy Difunctional or less epoxy compounds such as fluorinated novolaks and alicyclic diepoxides;
Examples include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl esters of aromatic polyols, urethane polyepoxy compounds, and epoxy compounds having three or more functional groups such as polyepoxy polybutadiene and the like. Be
Commercial products of epoxy compounds include EPICLON (registered trademark) 840 (DIC Corporation).

Examples of oxetane compounds include 3-ethyl-3-hydroxymethyl-1-oxetane, 1,4 bis [3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3-ethyl-3-phenoxymethyl-oxetane, bis ([ 1-ethyl (3-oxetanyl)] methyl) ether, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-ethyl-[(triethoxysilylpropoxy) methyl] oxetane, 3,3-dimethyl -2- (p-methoxyphenyl) -oxetane and the like.

As a block isocyanate compound, the compound which inactivated the isocyanate compound with the blocking agent (active hydrogen containing compound) is mentioned.
As an isocyanate compound, for example, hexamethylene diisocyanate, isophorone diisocyanate, toluyl diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate trimer, trimethylhexylylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, takenate (registration Commercially available isocyanates such as trademarks; Mitsui Chemicals, Inc.), Duranate (registered trademark; Asahi Kasei Corporation), Bayhydur (registered trademark; Bayer AG), etc., or difunctional or higher functional isocyanates combining these are preferred.

As the blocking agent, lactam [eg ε-caprolactam, δ-valerolactam, γ-butyrolactam etc.], oxime [eg acetoxime, methyl ethyl keto oxime (MEK oxime), methyl isobutyl keto oxime (MIBK oxime), cyclohexanone oxime etc] , Amines [eg aliphatic amines (dimethylamine, diisopropylamine, di-n-propylamine, diisobutylamine etc.), alicyclic amines (methylhexylamine, dicyclohexylamine etc.), aromatic amines (aniline, diphenylamine etc.)], Aliphatic alcohols [eg methanol, ethanol, 2-propanol, n-butanol etc], phenols and alkylphenols [eg phenol, cresol, ethylphenol, n-propylphenol , Isopropylphenol, n-butylphenol, octylphenol, nonylphenol, xylenol, diisopropylphenol, di-t-butylphenol etc.], imidazole [eg imidazole, 2-methylimidazole etc.], pyrazole [eg pyrazole, 3-methylpyrazole, 3, 5-dimethylpyrazole, etc., imine [eg ethyleneimine, polyethyleneimine etc.], active methylene [eg dimethyl malonate, diethyl malonate, diisopropyl malonate, acetylacetone, methyl acetoacetate, ethyl acetoacetate etc.], JP-A-2002- Examples thereof include the blocking agents described in Japanese Patent Application Laid-Open No. 309217 and Japanese Patent Application Laid-Open No. 2008-239890, and mixtures of two or more of these. Among them, as the blocking agent, oxime, lactam, pyrazole, active methylene or amine is preferable.

As the blocked isocyanate compound, commercially available commercial products may be used. For example, Trixene (registered trademark) BI7982, BI7641, BI7642, BI7950, BI7960, BI7991 and the like (Baxenden Chemicals LTD), Bayhydur (registered trademark; Bayer AG) Company) is preferably used. In addition, the compound group described in paragraph 0064 of WO 2015/158654 is also suitably used.

The specific particle containing the specific polymer described above and the polymerizable monomer described above can be produced, for example, by emulsifying a mixture of an oil phase component containing the specific polymer and the polymerizable monomer and an aqueous phase component. .

(Photopolymerization initiator)
The specific particles may contain at least one photopolymerization initiator.
When the specific particle contains a photopolymerizable monomer (for example, a radically polymerizable monomer), the specific particle preferably contains at least one kind of a photopolymerization initiator.

When the specific particles contain a photopolymerization initiator, the sensitivity to light (i.e., active energy ray) is high, and an image having an excellent hardness and an excellent adhesion to a substrate can be obtained.
In particular, when the specific particle contains a photopolymerization initiator, one specific particle has both a photopolymerizable monomer and a photopolymerization initiator. For this reason, since the distance between the photopolymerizable monomer and the photopolymerization initiator is close, the curing sensitivity of the film (hereinafter, also simply referred to as “sensitivity”) as compared with the case of using a conventional photocurable composition. ) Improves. As a result, a film which is more excellent in hardness and more excellent in adhesion to a substrate is formed.

Furthermore, when specific particles contain a photopolymerization initiator, it has been difficult to use a photopolymerization initiator (for example, water solubility), which has high sensitivity but low dispersibility or low solubility in water. Can be used at 25 ° C. in an amount of 1.0 mass% or less. This broadens the choice of the photoinitiator to be used and thus also broadens the choice of the light source used. For this reason, curing sensitivity can be improved more than before.
Specific examples of the above-mentioned photopolymerization initiators that have high sensitivity but low dispersibility or solubility in water but are difficult to use include the carbonyl compounds and acyl phosphine oxide compounds described below. And acyl phosphine oxide compounds are preferred.
Thus, the ink of the present disclosure can be contained in the ink of the present disclosure, which is a water-based composition, by including a substance having low water solubility in the specific particles. This is also one of the advantages of the ink of the present disclosure.

In addition, the ink of the embodiment in which the specific particles contain a photopolymerization initiator is excellent in storage stability as compared with the conventional photocurable composition. The reason is considered to be that aggregation or sedimentation of the photopolymerization initiator is suppressed by containing the photopolymerization initiator in the specific particles.

As a photoinitiator which may be contained in specific particle | grains, a well-known photoinitiator can be selected suitably and can be used.
The photopolymerization initiator is a compound that absorbs light (that is, active energy rays) to generate a radical which is a polymerization initiation species.

Although a well-known compound can be used as a photoinitiator, As a preferable photoinitiator, (a) Carbonyl compounds, such as aromatic ketones, (b) Acyl phosphine oxide compounds, (c) Aromatic onium salt compounds, (D) organic peroxide, (e) thio compound, (f) hexaarylbiimidazole compound, (g) ketoxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, k) Active ester compounds, (l) compounds having a carbon halogen bond, (m) alkylamine compounds and the like.

These photopolymerization initiators may be used alone or in combination of two or more of the compounds (a) to (m).

As preferable examples of (a) a carbonyl compound, (b) an acyl phosphine oxide compound, and (e) a thio compound, “RADIATION CURE IN POLYMER SCIENCE AND TECHNOLOGY”, J. P. FOUASSIER, J.J. F. RABEK (1993), pp. And compounds having a benzophenone skeleton or a thioxanthone skeleton described in 77 to 117, and the like.
More preferable examples include an α-thiobenzophenone compound described in JP-B-47-6416, a benzoin ether compound described in JP-B-47-3981, an α-substituted benzoin compound described in JP-B-47-22326, and Benzoin derivatives described in JP-A-47-23664; aroyl phosphonic acid esters disclosed in JP-A-57-30704; dialkoxybenzophenones described in JP-B-60-26483; JP-B-60-26403; Benzoin ethers described in JP-A-62-81345, JP-B1-34242, U.S. Pat. No. 4,318,791 pamphlet, .alpha.-aminobenzophenones described in EP-A-0284561 A1, JP-A-2-211452 P-di (dimethylamino) described in Nzoyl) benzene, thio-substituted aromatic ketone described in JP-A-61-194062, acyl phosphine sulfide described in JP-B-2-9597, acyl phosphine described in JP-B-2-9596, JP-B-63-61950 Thioxanthones described in Japanese Patent Application Publication No. Hei 5 (1995), coumarins described in Japanese Patent Publication No. 59-42864, and the like can be mentioned.
In addition, a polymerization initiator described in JP-A 2008-105379 or JP-A 2009-114290 is also preferable.

Examples of commercial products of the photopolymerization initiator include IRGACURE (registered trademark) 184, 369, 500, 651, 819, 907, 1000, 1300, 1700, 1870, DAROCUR (registered trademark) 1173, 2959, 4265, ITX, LUCIRIN (registered trademark) TPO [above, all made by BASF Corporation], ESACURE (registered trademark) KTO 37, KTO 46, KIP 150, EDB [all, all by Lamberti], H-Nu (registered trademark) 470, 470X [all, all Spectra Group Limited], Omnipol TX, 9210 [all of which are all IGM Resins B. V. And SPEEDCURE 7005, 7010, and 7040 (manufactured by LAMBSON Co., Ltd.).

Among these photopolymerization initiators, (a) a carbonyl compound or (b) an acylphosphine oxide compound is more preferable, and specifically, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (eg, BASF) IRGACURE (registered trademark) 819), 2- (dimethylamine) -1- (4-morpholinophenyl) -2-benzyl-1-butanone (for example, IRGACURE (registered trademark) 369 manufactured by BASF Corp.) 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, IRGACURE (registered trademark) 907 manufactured by BASF Corp.), 1-hydroxy-cyclohexyl-phenyl-ketone (for example, BASF Corp.) IRGACURE® 184), 2,4,6-trimethyl Nzoiru - diphenyl - phosphine oxide (e.g., DAROCUR (R) TPO, LUCIRIN (TM) TPO (all manufactured by BASF)), and the like.
Among these, from the viewpoint of sensitivity improvement and compatibility with LED light, as the encapsulated photopolymerization initiator (b), an acyl phosphine oxide compound is preferable, and a monoacyl phosphine oxide compound (particularly preferably 2, More preferred is 4,6-trimethylbenzoyl-diphenyl-phosphine oxide) or a bisacylphosphine oxide compound (particularly preferably bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide).
As a wavelength of LED light, 355 nm, 365 nm, 385 nm, 395 nm, or 405 nm is preferable.

In addition, from the viewpoint of suppressing migration, as the photopolymerization initiator, a polymer type photopolymerization initiator is also preferable.
As a polymeric photoinitiator, the above-mentioned Omnipol TX, 9210; SPEEDCURE 7005, 7010, 7040; is mentioned.

A specific particle containing a photopolymerization initiator can be produced, for example, by emulsifying a mixture of an aqueous phase component and an oil phase component containing a specific polymer, a photopolymerizable monomer, and a photopolymerization initiator. it can.

The content of the photopolymerization initiator is preferably 0.1% by mass to 25% by mass, more preferably 0.5% by mass to 20% by mass, still more preferably 1% by mass, based on the total solid content of the specific particles. It is ̃15% by mass.

(Sensitizer)
The specific particles may contain at least one sensitizer.
When the specific particles contain at least one photopolymerization initiator, the specific particles preferably contain at least one sensitizer.
When the specific particles contain a sensitizer, the decomposition of the photopolymerization initiator by irradiation of light (ie, active energy ray) can be further promoted.
A sensitizer is a substance that absorbs a specific activation energy ray to be in an electronically excited state. The sensitizer in the electronically excited state comes into contact with the photopolymerization initiator to produce actions such as electron transfer, energy transfer, heat generation, and the like. This promotes chemical change of the photopolymerization initiator, that is, decomposition, formation of radicals, acid or base, and the like.

Examples of the sensitizer include benzophenone, thioxanthone, isopropyl thioxanthone, anthraquinone, 3-acyl coumarin derivative, terphenyl, styryl ketone, 3- (aroyl methylene) thiazoline, camphor quinone, eosin, rhodamine, erythrosine and the like. .
Moreover, as a sensitizer, the compound represented by General formula (i) of Unexamined-Japanese-Patent No. 2010-24276, and the compound represented by General Formula (I) of Unexamined-Japanese-Patent No. 6-107718 are mentioned. Can also be suitably used.
Among the above, at least one selected from thioxanthone, isopropylthioxanthone, and benzophenone is preferable as the sensitizer from the viewpoint of compatibility with LED light and reactivity with a photopolymerization initiator, and from thioxanthone and isopropyl thioxanthone At least one selected is more preferable, and isopropylthioxanthone is more preferable.
When the specific particle contains a sensitizer, it may contain one sensitizer alone, or two or more sensitizers.

When the specific particles contain a sensitizer, the content of the sensitizer is preferably 0.1% by mass to 20% by mass, and 0.2% by mass to 15% by mass with respect to the total solid content of the specific particles. %, More preferably 0.3% by mass to 10% by mass.

Specific particles containing a photopolymerization initiator and a sensitizer include, for example, a mixture of an oil phase component containing a specific polymer, a photopolymerizable monomer, a photopolymerization initiator, and a sensitizer and an aqueous phase component. It can be produced by emulsifying.

(Photothermal conversion agent)
When the specific particles contain a thermally polymerizable monomer as the polymerizable monomer, the specific particles may contain at least one photothermal conversion agent.
The photothermal conversion agent is a compound that absorbs infrared rays and generates heat to polymerize and cure the thermally polymerizable monomer. As the photothermal conversion agent, known compounds can be used.

As a photothermal conversion agent, an infrared absorber is preferable. Examples of infrared absorbers include polymethylindolium, indocyanine green, polymethine dyes, croconium dyes, cyanine dyes, merocyanine dyes, squarylium dyes, chalcogenopyryloarylidene dyes, metal thiolate complex dyes, bis (chalcogenopirillo) polymethine dyes And oxyindolizine dyes, bisaminoallyl polymethine dyes, indolizine dyes, pyrylium dyes, quinoid dyes, quinone dyes, phthalocyanine dyes, naphthalocyanine dyes, azo dyes, azomethine dyes, carbon black and the like.

Specific particles containing a photothermal conversion agent can be produced, for example, by emulsifying a mixture of an oil phase component containing a specific polymer, a thermally polymerizable monomer, and a photothermal conversion agent, and an aqueous phase component.

A photothermal conversion agent may be used individually by 1 type, and may use 2 or more types together.
The content of the photothermal conversion agent is preferably 0.1% by mass to 25% by mass, and more preferably 0.5% by mass to 20% by mass, with respect to the total solid content of the specific particles. It is more preferable that the content is 15% by mass.

(Thermosetting accelerator)
When the specific particles contain a thermally polymerizable monomer as a polymerizable monomer, the specific particles may contain at least one of a heat curing accelerator.
The thermal curing accelerator is a compound that catalytically accelerates the thermal curing reaction of the thermally polymerizable monomer.

Known compounds can be used as the heat curing accelerator. The heat curing accelerator is preferably an acid or a base, or a compound which generates an acid or a base by heating, for example, a carboxylic acid, a sulfonic acid, a phosphoric acid, an aliphatic alcohol, a phenol, an aliphatic amine, an aromatic amine, an imidazole (For example, phenylimidazole, 2-methylimidazole), pyrazole and the like.

A specific particle containing a heat curing accelerator may be produced, for example, by emulsifying a mixture of an oil phase component containing a specific polymer, a heat polymerizable monomer, and a heat curing accelerator, and an aqueous phase component. it can.

The heat curing accelerator may be used alone or in combination of two or more.
The content of the thermosetting accelerator is preferably 0.1% by mass to 25% by mass, and more preferably 0.5% by mass to 20% by mass, with respect to the total solid content of the specific particles. More preferably, it is 1% by mass to 15% by mass.

In the ink of the present disclosure, the total solid content of the specific particles is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more based on the total solid content of the ink. Is more preferably 80% by mass or more, and still more preferably 85% by mass or more.
Thereby, the dispersion stability is further improved, and the adhesion between the image and the substrate is further improved.

In the ink of the present disclosure, the total solid content of the specific particles is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, with respect to the total amount of the ink, and 5% by mass. More preferably, it is from 30% by mass.
When the total solid content of the specific particles is 1% by mass or more with respect to the total amount of the ink, the adhesion between the image and the substrate is further improved.
In addition, when the total solid content of the specific particles is 50% by mass or less based on the total amount of the ink, the dispersion stability of the ink is further improved.

The volume average dispersed particle size of the specific particles is not particularly limited, but is preferably 0.01 μm to 10.0 μm, more preferably 0.01 μm to 5 μm, from the viewpoint of dispersion stability, more preferably 0.05 μm. It is further preferably 1 to 1 μm, more preferably 0.05 μm to 0.5 μm, and still more preferably 0.05 μm to 0.3 μm.
In the present specification, the "volume-average dispersed particle size" refers to a value measured by a light scattering method. The measurement of the volume average dispersed particle diameter of the specific particles by the light scattering method is performed using, for example, LA-960 (Horiba, Ltd.).

<Water>
The ink of the present disclosure contains water.
Water is a dispersion medium for specific particles (dispersoids).
The content of water in the ink of the present disclosure is not particularly limited, but the content of water is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 95% by mass, based on the total amount of the ink % By mass, more preferably 30% by mass to 90% by mass, and particularly preferably 50% by mass to 90% by mass.

<Colorant>
The ink of the present disclosure may be an ink containing at least one colorant (so-called "colored ink") or an ink not containing a colorant (so-called "clear ink").
When the ink contains a coloring material, the coloring material is preferably contained outside the specific particle (that is, the specific particle does not contain the coloring material).
The colorant is not particularly limited, and may be selected from known colorants such as pigments, water-soluble dyes and disperse dyes. Among these, from the viewpoint of excellent weather resistance and rich color reproducibility, it is more preferable to include a pigment.

The pigment is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include known organic pigments and inorganic pigments, and resin particles dyed with a dye, commercially available pigment dispersions and surfaces Treated pigments (for example, pigments in which the pigment is dispersed in water, a liquid compound, an insoluble resin or the like as a dispersion medium, or pigments having a pigment surface treated with a resin or a pigment derivative or the like) can also be mentioned.
Examples of organic pigments and inorganic pigments include yellow pigments, red pigments, magenta pigments, blue pigments, cyan pigments, green pigments, orange pigments, purple pigments, brown pigments, black pigments, white pigments, and the like.

When a pigment is used as the colorant, a pigment dispersant may be used as necessary.
When a pigment is used as the coloring material, a self-dispersible pigment having a hydrophilic group on the surface of the pigment particle may be used as the pigment.
With regard to the colorant and the pigment dispersant, paragraphs 0180 to 0200 of JP-A-2014-040529 and paragraphs 0122 to 0129 of WO 2016/052052 can be referred to as appropriate.

When the ink of the present disclosure contains a colorant, the content of the colorant is preferably 0.1% by mass to 20% by mass, and more preferably 0.5% by mass to 10% by mass, with respect to the total amount of the ink. 5% to 5% by weight is particularly preferred.

<Other ingredients>
The ink of the present disclosure may optionally contain other components other than those described above.
The other components may be contained in the specific particle or may not be contained in the specific particle.

(Organic solvent)
The ink of the present disclosure may contain an organic solvent.
When the ink of the present disclosure contains an organic solvent, the adhesion between the image and the substrate can be further improved.
When the ink of the present disclosure contains an organic solvent, the content of the organic solvent is preferably 0.1% by mass to 10% by mass with respect to the total amount of the ink, and 0.1% by mass to 5% by mass It is more preferable that
Specific examples of the organic solvent are as follows.
・ Alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol etc.)
Polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, 2- Methyl propane diol etc.)
· Polyhydric alcohol ethers (eg ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, tripropylene Glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol Monophenyl ether, propylene glycol monophenyl ether)
· Amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, penta) Methyl diethylene triamine, tetramethyl propylene diamine etc.)
· Amides (eg formamide, N, N-dimethylformamide, N, N-dimethylacetamide etc.)
・ Heterocycles (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone etc.)
・ Sulphoxides (eg, dimethyl sulfoxide etc.)
· Sulfones (eg, sulfolane etc.)
・ Others (urea, acetonitrile, acetone etc.)

(Surfactant)
The ink of the present disclosure may contain at least one surfactant.
When the ink of the present disclosure contains a surfactant, the wettability of the ink to the substrate is improved.
As the surfactant, for example, higher fatty acid salt, alkyl sulfate, alkyl ester sulfate, alkyl sulfonate, alkyl benzene sulfonate, sulfosuccinate, naphthalene sulfonate, alkyl phosphate, polyoxyalkylene alkyl ether Phosphate, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, polyoxyethylene fatty acid amide, amine oxide and the like can be mentioned.
Among these, as the surfactant, at least one surfactant selected from alkyl sulfates, alkyl sulfonates and alkyl benzene sulfonates is preferable, and alkyl sulfates are particularly preferable.
The surfactant is preferably an alkyl sulfate having an alkyl chain length of 8 to 18 from the viewpoint of dispersibility of specific particles, and sodium dodecyl sulfate (SDS, alkyl chain length: 12) and sodium cetyl sulfate (SCS) And at least one selected from alkyl chain length: 16).

In addition, as surfactants other than the above-mentioned surfactants, those described in JP-A-62-173463 and JP-A-62-183457 can also be mentioned. For example, as other surfactants, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers, siloxanes, etc. It can be mentioned.
Moreover, organic fluoro compounds are also mentioned as surfactant.
The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include fluoro surfactant, oily fluoro compound (for example, fluoro oil), and solid fluoro compound resin (for example, tetrafluoroethylene resin), and JP-B-57-9053 Those described in columns 8 to 17) and JP-A-62-135826 may be mentioned.

In addition, the ink of the present disclosure can also contain substantially no surfactant (for example, an anionic surfactant).
Here, "does not substantially contain" indicates that the content is less than 1% by mass (preferably less than 0.1% by mass) based on the total amount of the ink.
The embodiment in which the ink substantially does not contain an anionic surfactant has an advantage that the foaming of the ink can be suppressed, an advantage that the water resistance of the image can be improved, an advantage that the whitening due to the bleed out after the image formation can be suppressed, etc. Have. Further, in particular, when using a pigment dispersion having an anionic dispersing group for the preparation of the ink, the anionic surfactant increases the ion concentration in the system, and the ionization degree of the anionic pigment dispersant decreases. Therefore, it also has the advantage of being able to suppress the decrease in the dispersibility of the pigment.

(Polymerization inhibitor)
The ink of the present disclosure may contain a polymerization inhibitor.
When the ink of the present disclosure contains a polymerization inhibitor, the storage stability of the ink may be further improved.
Examples of polymerization inhibitors include p-methoxyphenol, quinones (eg, hydroquinone, benzoquinone, methoxybenzoquinone etc.), phenothiazine, catechols, alkylphenols (eg, dibutyl hydroxytoluene (BHT) etc.), alkyl bisphenols, dimethyldithiocarbamine Acid zinc, dimethyldithiocarbamic acid copper, dibutyldithiocarbamic acid copper, salicylic acid copper, thiodipropionic acid esters, mercaptobenzimidazole, phosphites, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 2,2,6,6-Tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL), cuperone Al, tris (N-nitroso-N-phenylhydroxylamine) aluminum salt And the like.
Among these, at least one selected from p-methoxyphenol, catechols, quinones, alkylphenols, TEMPO, TEMPOL, cuperone Al, and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt is preferable, and p More preferred is at least one selected from methoxyphenol, hydroquinone, benzoquinone, BHT, TEMPO, TEMPOL, cuperone Al, and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.

(UV absorber)
The ink of the present disclosure may contain a UV absorber.
When the ink of the present disclosure contains a UV absorber, the weather resistance and the like of the image can be further improved.
As a ultraviolet absorber, well-known ultraviolet absorbers, for example, a benzotriazole type compound, a benzophenone series compound, a triazine type compound, a benzoxazole type compound, etc. are mentioned.

In addition, the ink of the present disclosure may be a polymerizable monomer, a photopolymerization agent, or the like outside the specific particle, as needed, from the viewpoint of image hardness, adhesion between the image and the substrate, and control of ink discharge stability. It may contain an initiator, a resin and the like.
It is preferable that these components have water solubility or water dispersibility.
Here, "water-soluble" refers to a property in which the amount of dissolution with respect to 100 g of distilled water at 25 ° C. exceeds 1 g when dried at 105 ° C. for 2 hours.
Also, "water dispersible" refers to the property of being water insoluble and dispersed in water. Here, "water insoluble" refers to the property that the amount of dissolution in 100 g of distilled water at 25 ° C. is 1 g or less when dried at 105 ° C. for 2 hours.
Further, "the ink contains a polymerizable monomer outside the specific particle" means that the ink contains a polymerizable monomer which is not contained in the specific particle. The same applies to the case where the photopolymerization initiator, the water-soluble resin, the water-dispersible resin and the like are contained outside the specific particles.

Examples of the polymerizable monomer that can be contained outside the specific particle include the polymerizable monomers described in paragraphs [0148] to [0156] of WO 2016/052053.
As polymerizable monomers that can be contained outside the specific particles, compounds having an ethylenically unsaturated group, radically polymerizable monomers such as acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, unsaturated urethane, etc. It can be mentioned.
Among these, as a polymerizable monomer that can be contained outside the specific particle, a compound having an ethylenically unsaturated group is preferable, and a compound having a (meth) acryloyl group is particularly preferable.

From the viewpoint of water solubility or water dispersibility, the polymerizable monomer that can be contained outside the specific particle is selected from the group consisting of an amide structure, a polyethylene glycol structure, a polypropylene glycol structure, a carboxyl group, and a salt of a carboxy group. Compounds having at least one type are preferred.

From the viewpoint of water solubility or water dispersibility, examples of the polymerizable monomer that can be contained outside the specific particle include, for example, (meth) acrylic acid, sodium (meth) acrylate, potassium (meth) acrylate, N, N- Dimethyl acrylamide, N, N-diethyl acrylamide, morpholine acrylamide, N-2-hydroxyethyl (meth) acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, glycerol monomethacrylate, N- [tris (3-acryloylaminopropyloxymethylene) methyl] acrylamide, diethylene glycol bis (3-acryloylaminopropyl) ether Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, compounds represented by the following general formula (a) to general formula (d), and ethoxylated trimethylolpropane triacrylate (for example, SR 9035 manufactured by Sartomer Corporation) (Meth) acrylic acid, N, N-dimethyl acrylamide, N-2-hydroxyethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, glycerin monomethacrylate, N- [] Tris (3-acryloylaminopropyloxymethylene) methyl] acrylamide, diethylene glycol bis (3-acryloylaminopropyl) ether, polyethylene glycol di (meth) acrylate, and polypropylene glycol Of at least one selected from an aryldi (meth) acrylate, a compound represented by the following general formula (a) to a general formula (d), and an ethoxylated trimethylolpropane triacrylate (for example, SR9035 manufactured by Sartomer Corporation) .

In general formula (a), a plurality of R ^{1 's} each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, a plurality of R ^{2' s} each independently represent a hydrogen atom or a methyl group; Each L ¹ independently represents a single bond or a divalent linking group.
In the general formula (b), a plurality of R ^{3 's} each independently represent a hydrogen atom or a methyl group, a plurality of L ^{2' s} each independently represent an alkylene group having 1 to 8 carbon atoms, a plurality of k and p Each independently represents 0 or 1, and a plurality of m each independently represent an integer of 0 to 8, provided that at least one of k and p is 1.
In general formula (c), a plurality of R ^{4 's} each independently represent a hydrogen atom or a methyl group, a plurality of n's each independently represent an integer of 1 to 8 and 1 represents an integer of 0 or 1.
In formula (d), Z ¹ represents a residue obtained by removing q hydrogen atoms from a hydroxyl group of a polyol, q represents an integer of 3 to 6, and plural R ^{5 s} each independently represent a hydrogen atom or methyl And a plurality of L ³ each independently represent an alkylene group having 1 to 8 carbon atoms.

Specific examples of the compounds represented by the general formulas (a) to (d) include compounds represented by the following AM-1 to AM-4.

The above AM-1 to AM-4 can be synthesized by the method described in Patent No. 5591858.

With regard to the photopolymerization initiator and the resin that can be contained outside the specific particle, reference can be made to paragraphs 0139 to 0147 and 0157 of WO 2016/052053 as appropriate.

<Preferred physical properties of ink>
The ink of the present disclosure preferably has a viscosity of 3 mPa · s to 15 mPa · s, more preferably 3 mPa · s to 13 mPa · s, when the ink is 25 ° C. to 50 ° C. In particular, the ink of the present disclosure preferably has a viscosity of 50 mPa · s or less when the ink is at 25 ° C. When the viscosity of the ink is in the above range, higher ejection stability can be realized.
The viscosity of the ink is a value measured using a viscometer (VISCOMETER TV-22, Toki Sangyo Co., Ltd.).

The ink of the present disclosure can be used for image formation by a coating method, an immersion method, a gravure method, a flexo method, an inkjet method and the like.
The ink of the present disclosure is particularly preferably used for image formation by an inkjet method (i.e., used as an inkjet ink).

In the case where the ink of the present disclosure is a photocurable ink or a thermosetting ink, particularly preferred embodiments include the following Forms 1 to 4.

<Form 1>
Form 1 is a photocurable ink in which the specific particles contain a photopolymerizable monomer and the specific polymer is a specific linear polymer.
In the form 1, it is preferable that Mw of a specific chain polymer is 5000 or more. For the more preferable range of Mw of the specific chain polymer, the preferable range of the molecular weight of the specific polymer described above can be referred to.
In Form 1, the molecular weight of the photopolymerizable monomer is preferably 100 to 4000. The more preferable range of the molecular weight of the above-mentioned polymerizable monomer can be referred to for the more preferable range of the molecular weight of a photopolymerizable monomer.

<Form 2>
Form 2 is a photocurable ink in which the specific particles contain a photopolymerizable monomer and the specific polymer is a specific crosslinked polymer.
As Form 2, it is preferable that the specific particle is a microcapsule including a shell made of a specific crosslinked polymer having a three-dimensional crosslinked structure, and a core containing a photopolymerizable monomer.
In Form 2, the molecular weight of the photopolymerizable monomer is preferably 100 to 4000. The more preferable range of the molecular weight of the above-mentioned polymerizable monomer can be referred to for the more preferable range of the molecular weight of a photopolymerizable monomer.

<Form 3>
Form 3 is a thermosetting ink in which the specific particle contains a thermally polymerizable monomer and the specific polymer is a specific linear polymer.
In the form 3, it is preferable that Mw of a specific chain polymer is 5000 or more. For the more preferable range of Mw of the specific chain polymer, the preferable range of the molecular weight of the specific polymer described above can be referred to.
In Form 3, the molecular weight of the thermally polymerizable monomer is preferably 100 to 4000. For the more preferable range of the molecular weight of the thermally polymerizable monomer, the more preferable range of the molecular weight of the above-mentioned polymerizable monomer can be referred to.

<Form 4>
Form 4 is a thermosetting ink in which the specific particles contain a thermally polymerizable monomer and the specific polymer is a specific crosslinked polymer.
As Form 4, it is preferable that the specific particle is a microcapsule including a shell made of a specific crosslinked polymer having a three-dimensional crosslinked structure, and a core containing a thermally polymerizable monomer.
In Form 4, the molecular weight of the thermally polymerizable monomer is preferably 100 to 4000. For the more preferable range of the molecular weight of the thermally polymerizable monomer, the more preferable range of the molecular weight of the above-mentioned polymerizable monomer can be referred to.

[One Example of Method of Producing Ink (Procedure A)]
Although there is no restriction | limiting in particular in the method to manufacture the ink of this indication, An example (the manufacturing method A) of the following is mentioned.
Production method A has a step of forming specific particles by mixing and emulsifying an oil phase component containing an organic solvent and a specific polymer, and an aqueous phase component containing water.

In the step of forming specific particles, specific particles are formed by mixing the above-described oil phase component and aqueous phase component and emulsifying the obtained mixture. The specific particles formed function as dispersoids in the manufactured ink.
Water in the water phase component functions as a dispersion medium in the manufactured ink.

Examples of the organic solvent contained in the oil phase component include ethyl acetate and methyl ethyl ketone.
At least a part of the organic solvent is preferably removed in the process of forming the specific particles and after the formation of the specific particles.

The oil phase component may be, for example, a polymerizable monomer, a photopolymerization initiator, a sensitizer, a compound for introducing a polymerizable group (preferably a compound having a polymerizable group and an active hydrogen group), polymerization, in addition to the above components. It may include an isocyanate compound having a functional group introduced, an isocyanate compound having a hydrophilic group introduced, and the like.

The water phase component is not particularly limited except that it contains water, and may be water alone.
The water phase component may contain components other than water.
For example, the aqueous phase component may contain a compound for introducing a hydrophilic group (preferably, a compound having a hydrophilic group and an active hydrogen group).
The aqueous phase component may also contain a basic compound as a neutralizing agent for non-neutralized anionic groups (carboxy, sulfo, phosphoric, phosphonic, sulfuric, etc.) . Thereby, in the process of forming a specific particle, an anionic group neutralized (ie, an anionic group in the form of a salt; eg, a salt of a carboxy group, a salt of a sulfo group, a salt of a phosphoric acid group, a phosphonic acid group) Salts of sulfuric acid groups, etc.).
When using the said basic compound (neutralizing agent), it is preferable to make the said basic compound (neutralizing agent) contain at least an aqueous phase component.
Examples of the basic compound include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine. Among these, as the basic compound, an inorganic base such as sodium hydroxide or potassium hydroxide is preferable.
Further, as a salt in the form of a salt in the form of an anionic group, alkali metal salts such as sodium salt and potassium salt; organic amine salts such as triethylamine salt and the like can be mentioned. Among these, as the salt in the form of a salt in the form of a salt, alkali metal salts such as sodium salt and potassium salt are preferable.

The total amount of the oil phase component and the water phase component excluding the organic solvent and water in the production method A corresponds to the total solid content of the specific particles in the manufactured ink.
For the preferable range of the amount of each component that can be used in the production method A, the above-mentioned "ink" can be referred to. In this reference, "content" and "total solid content of specific particles" in the section of "ink" described above are respectively "amount used" and "oil phase component and water phase component from organic solvent and water It is read as "the total amount excluding".

In the step of forming the specific particles, the method of mixing the oil phase component and the water phase component is not particularly limited, and examples thereof include mixing by stirring.

In the step of forming the specific particles, the method of emulsification is not particularly limited, and examples thereof include emulsification with an emulsification device such as a homogenizer (for example, a dispersing machine or the like).
The rotation speed of the disperser in emulsification is, for example, 5000 rpm (round per minute) to 20000 rpm, preferably 10000 rpm to 15000 rpm.
The rotation time in emulsification is, for example, 1 minute to 120 minutes, preferably 3 minutes to 60 minutes, more preferably 3 minutes to 30 minutes, and still more preferably 5 minutes to 15 minutes.

Emulsification in the step of forming the specific particles may be performed under heating.
By carrying out the emulsification under heating, specific particles can be formed more efficiently.
In addition, by performing emulsification under heating, at least a portion of the organic solvent in the oil phase component can be easily removed from the mixture.
The heating temperature in the case of performing the emulsification under heating is preferably 35 ° C. to 70 ° C., and more preferably 40 ° C. to 60 ° C.

Also, the step of forming the specific particles includes an emulsification step of emulsifying the mixture (for example, at a temperature of less than 35 ° C.), and a heating step of heating the emulsion obtained by the emulsification step (for example, at a temperature of 35 ° C. or more) , May be included.
In the aspect including the emulsification step and the heating step, it is possible to form the specific particles more efficiently particularly in the heating step.
In the embodiment including the emulsification step and the heating step, particularly at the heating step, it is easy to remove at least a part of the organic solvent in the oil phase component from the mixture.
The heating temperature in the heating step is preferably 35 ° C. to 70 ° C., and more preferably 40 ° C. to 60 ° C.
The heating time in the heating stage is preferably 6 hours to 50 hours, more preferably 12 hours to 40 hours, and still more preferably 15 hours to 35 hours.

Moreover, the manufacturing method A may have other processes other than the process of forming specific particle | grains as needed.
As another process, the process of adding other components (a pigment etc.) after the process of forming specific particle | grains is mentioned.
The other components to be added (such as pigments) are as already described as the other components that may be contained in the ink.

[Another example of the method for producing the ink (production method B)]
As a method of producing an ink of an embodiment containing specific particles containing a specific crosslinked polymer, Production Method B shown below is also suitable.
Production method B mixes an oil phase component containing an organic solvent and a trifunctional or higher isocyanate compound with an aqueous phase component containing water, and the presence of a specific gelling agent (ie, a gelling agent having an active hydrogen group) It has the process of forming specific particle | grains by emulsifying below.
A preferred embodiment of Preparation method B is that an oil phase component is not a specific polymer but a trifunctional or higher isocyanate compound is used, and a mixture of an oil phase component and an aqueous phase component is emulsified in the presence of a specific gelling agent Except for the same as the preferred embodiment of Preparation A.
A more preferred embodiment of Preparation B uses an aqueous phase component containing water and a specific gelling agent as an aqueous phase component, and a mixture of an oil phase component and an aqueous phase component is contained in the aqueous phase component. It is an aspect made to emulsify in presence of an agent.

[Image forming method]
In the image forming method of the present disclosure, a step of forming an ink film by applying the above-described ink of the present disclosure onto a substrate (hereinafter, also referred to as “application step”) and a step of heating the ink film ( Hereinafter, it is also referred to as “heating step”).
The image forming method of the present disclosure may have other steps as necessary.
According to the image forming method of the present disclosure, an image excellent in scratch resistance is formed on a substrate.

(Applying process)
The application step is a step of forming an ink film by applying the ink of the present disclosure on a substrate.
As an aspect which applies an ink on a base material, you may employ | adopt any of the aspect using well-known methods, such as a coating method, an immersion method, and an inkjet method. Among them, the inkjet method is preferable in that a film (for example, an image) can be formed on various substrates (including a recording medium).

The substrate is not particularly limited, and, for example, known substrates provided as a support and a recording medium can be appropriately selected and used.
As the substrate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene etc.), metal plate (eg, a plate of metal such as aluminum, zinc, copper etc.), plastic film (eg, polychloride) Vinyl (PVC: Polyvinyl Chloride) resin, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, cellulose nitrate, polyethylene terephthalate (PET: Polyethylene Terephthalate), polyethylene (PE: Polyethylene), polystyrene (PS) : Polystyrene (polystyrene), polypropylene (PP), polycarbonate (PC: Polycarbonate), polyvinyl acetal, films such as acrylic resin, paper laminated or vapor-deposited with the metal mentioned above, metal mentioned above is laminated A plastic film which is to or deposited, and the like.

Moreover, a textiles base material is also mentioned as a base material.
Examples of the material of the textile base material include natural fibers such as cotton, silk, hemp and wool; chemical fibers such as viscose rayon and rheocel; synthetic fibers such as polyester, polyamide and acrylic; natural fibers, chemical fibers and synthetic Mixtures of at least two selected from the group consisting of fibers; and the like. As the textile substrate, the textile substrate described in paragraphs 0039 to 0042 of WO 2015/158592 may be used.

As a substrate, plastics such as polyvinyl chloride (PVC) substrate, polystyrene (PS) substrate, polycarbonate (PC) substrate, polyethylene terephthalate (PET) substrate, polypropylene (PP) substrate, acrylic resin substrate and the like Substrates are preferred.

The application of the ink by the inkjet method can be performed using a known inkjet recording device.
The ink jet recording apparatus is not particularly limited, and any known ink jet recording apparatus capable of achieving the target resolution can be selected and used.
Examples of the inkjet recording apparatus include an apparatus including an ink supply system, a temperature sensor, and a heating unit.
The ink supply system includes, for example, a main tank containing the ink of the present disclosure, a supply pipe, an ink supply tank immediately in front of an inkjet head, a filter, and a piezoelectric inkjet head. The piezo-type inkjet head preferably has 1 pl to 100 pl, more preferably 8 pl to 30 pl multi-size dots, preferably 320 dpi (dot per inch) x 320 dpi to 4000 dpi x 4000 dpi, more preferably 400 dpi x 400 dpi to 1600 dpi x 1600 dpi It can be driven to be able to discharge at a resolution of 720 dpi × 720 dpi, more preferably. In addition, dpi represents the number of dots per 2.54 cm (1 inch).

In addition, in the application step, the ink may be applied to a substrate that has been preheated.
In the application step, when the ink is applied to the preheated substrate, the following heating step can be performed by the heated substrate (that is, the ink film is formed by the heated substrate) Can be heated).
The heating of the substrate before applying the ink can be performed, for example, by the heating means exemplified in the heating step described later.

(Heating process)
The heating step is a step of heating the ink film formed on the substrate.
By heating the ink film in the heating step, as described above, thickening of the ink film occurs, and as a result, an image excellent in scratch resistance can be obtained.
In the image forming method of the present disclosure, when the above-described thermosetting ink is used as the ink of the present disclosure, curing of the ink film (that is, thermal polymerization by a thermally polymerizable monomer) is performed by heating in the heating step. May be In other words, when the above-described thermosetting ink is used as the ink of the present disclosure, the heating step may also serve as the curing step B described later.

As an aspect of the heating in a heating process, the aspect which heats the ink provided on the base material by a heating means is mentioned.
Further, as described above, when the ink is applied to the preheated substrate in the application step, an embodiment of heating the ink by the heated substrate may be mentioned as an embodiment of the heating in the heating step.

The heating means is not particularly limited, and examples thereof include a heat drum, a warm air, an infrared lamp, an infrared LED, an infrared heater, a thermal oven, a heat plate, an infrared laser, an infrared dryer and the like. Among them, a light emitting diode having an emission wavelength in the near infrared to far infrared rays, having a maximum absorption wavelength at a wavelength of 0.8 μm to 1.5 μm or 2.0 μm to 3.5 μm, from the point that the ink can be efficiently heat-cured An LED), a heater emitting near infrared to far infrared radiation, a laser having an emission wavelength of near infrared to far infrared radiation, or a dryer emitting near infrared to far infrared radiation is preferable.

The heating temperature during heating is preferably 40 ° C. or higher, more preferably 40 ° C. to 200 ° C., still more preferably 45 ° C. to 100 ° C., and further preferably 50 ° C. to 80 ° C. from the viewpoint of more effectively thickening the ink film. More preferably, 55 ° C to 70 ° C is more preferable.
The heating temperature refers to the temperature of the ink on the substrate, and can be measured by a thermograph using an infrared thermography device H2640 (manufactured by Nippon Avionics Co., Ltd.).
The heating time can be appropriately set in consideration of the heating temperature, the composition of the ink, the printing speed and the like. The heating time is preferably 5 seconds or more, more preferably 5 seconds to 5 minutes, more preferably 10 seconds to 1 minute, and still more preferably 20 seconds to 1 minute.

(Curing process)
The image forming method of the present disclosure can have a curing step of curing the ink film heated by the heating step.
By the curing step, a polymerization reaction (that is, a crosslinking reaction) by the polymerizable monomer proceeds in the ink film. Therefore, when the image forming method of the present disclosure has a curing step, the hardness of the image can be further improved, and thus the scratch resistance of the image can be further improved.

In the image forming method of the present disclosure, when a photocurable ink is used, the ink film is irradiated with light (that is, active energy ray) as the curing step by irradiating the ink film heated in the heating step. A curing step (hereinafter, "curing step A") for curing can be provided.

In the image forming method of the present disclosure, when a thermosetting ink is used, a curing step of subjecting the ink film heated in the heating step to heating or irradiation of infrared rays as a curing step to thermally cure the ink film ( Hereinafter, "hardening process B" can be provided.
However, when using a thermosetting ink, thickening and thermal curing of the ink film are performed by the above-described heating step without providing the curing step B (that is, the curing step B different from the above-described heating step). May be
That is, in the case of using a thermosetting ink in the image forming method of the present disclosure, a heating step for thickening the ink film and a curing step B for thermosetting the ink film may be separately provided. Alternatively, a single heating step may be provided to both thicken and thermally cure the ink film.

-Curing process A-
The curing step A is a step of curing the ink film by irradiating the ink film heated in the heating step with an active energy ray.
In the curing step A, the photocrosslinking reaction (that is, the photopolymerization reaction) of specific particles in the ink film proceeds by irradiating the ink film heated in the heating step with active energy rays, whereby the ink film is formed. The strength of the

As an active energy ray which can be used by hardening process A, an ultraviolet ray (UV light), a visible ray, an electron beam etc. are mentioned, Among these, UV light is preferred.

The peak wavelength of the active energy ray (light) is preferably 200 nm to 405 nm, more preferably 220 nm to 390 nm, and still more preferably 220 nm to 385 nm.
In addition, 200 nm to 310 nm is also preferable, and 200 nm to 280 nm is also preferable.

Exposure surface illuminance when the active energy ray (light) is irradiated, for example, ^{10mW / cm 2 ~ 2000mW / cm} 2, preferably ^{20mW / cm 2 ~ 1000mW / cm} 2.
The exposure energy when the active energy ray (light) is irradiated is, for example, 10 mJ / cm ² to 2000 mJ / cm ² , preferably 20 mJ / cm ² to 1000 mJ / cm ² .

As sources for generating active energy rays (light), mercury lamps, metal halide lamps, UV fluorescent lamps, gas lasers, solid lasers and the like are widely known.
Also, the replacement of the light source exemplified above with a semiconductor ultraviolet light emitting device is very useful both industrially and environmentally.
Among semiconductor ultraviolet light emitting devices, LEDs (Light Emitting Diodes) and LDs (Laser Diodes) are small in size, high in life, high in efficiency, and low in cost, and are expected as light sources.
As a light source, a metal halide lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, an LED or a blue-violet laser is preferable.
Among these, when using a sensitizer and a photopolymerization initiator in combination, an ultra-high pressure mercury lamp capable of light irradiation with a wavelength of 365 nm, 405 nm or 436 nm, light irradiation with a wavelength of 365 nm, 405 nm or 436 nm is possible A high pressure mercury lamp or an LED capable of light irradiation with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm or 405 nm is more preferable, and an LED capable of light irradiation with a wavelength of 355 nm, 365 nm, 385 nm, 395 nm or 405 nm is most preferable.

In the curing step A, the irradiation time of the active energy ray to the ink applied on the substrate is, for example, 0.01 seconds to 120 seconds, preferably 0.1 seconds to 90 seconds.
As the irradiation conditions and the basic irradiation method, the irradiation conditions and the irradiation methods disclosed in Japanese Patent Application Laid-Open No. 60-132767 can be similarly applied.
Specifically, a light source is provided on both sides of a head unit including an ink discharge device as an active energy ray irradiation method, and the head unit and the light source are scanned by a so-called shuttle method, or by another light source without driving. It is preferable to use an active energy ray irradiation method.
The irradiation of the active energy ray is preferably performed after a certain time (for example, 0.01 seconds to 120 seconds, preferably 0.01 seconds to 60 seconds) after the ink is landed and the heating and drying are performed.

-Curing process B-
The curing step B is a step of thermally curing the ink film by applying heat or irradiation of infrared rays to the ink film heated in the heating step.
In the curing step B, the thermal crosslinking reaction (that is, thermal polymerization reaction) of specific particles in the ink proceeds by heating or irradiating infrared rays to the ink film heated in the heating step, whereby the ink film The strength of the
The preferred embodiment of the curing step B is the same as the preferred embodiment of the heating step.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.
In the following, “parts” represents parts by mass unless otherwise specified.
Moreover, "*" in chemical formula represents a bonding position.

<Synthesis of Specific Chain Polymer>
(Synthesis of Polymer 1 (terminal, with photopolymerizable group))
According to the following reaction scheme, the following polymer 1 (terminal, with photopolymerizable group) was synthesized as a specific chain polymer.
Here, "terminal" means that the polymer has a monovalent gelling group at the end of the main chain, and "having a photopolymerizable group" means that the polymer has a photopolymerizable group. It means (it makes the same hereafter).

In a three-necked flask, dicyclohexylmethane-4,4'-diisocyanate (HMDI) (82.5 g), dimethylol propionic acid (DMPA) (16.9 g), tricyclodecane dimethanol (compound (2-5)) (2 9 g), bisphenol A epoxy diacrylate (compound (a-21)) (77.0 g), and ethyl acetate (102.3 g) were charged and heated to 70 ° C. Thereto, 0.2 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth catalyst; hereinafter, also referred to as “U-600”) was added, and the mixture was stirred at 70 ° C. for 5 hours.
Next, there, end capping agent is a particular gelling agent (specifically, amphiphilic gelling agent having an active hydrogen group) eicosyl amine as _{_{_{(C 20 H 41 NH 2)}}} (0.3g ) And ethyl acetate (190 g) were added and stirred at 70 ° C. for 3 hours. After stirring for 3 hours, the reaction solution was allowed to cool to room temperature and then adjusted in concentration with ethyl acetate to obtain a 30% by mass solution of polymer 1 (the solvent was ethyl acetate).
The weight average molecular weight (Mw) of the polymer 1 was 8000, and the acid value was 0.70 mmol / g.

The polymer 1 has an acryloyl group as a photopolymerizable group.
The polymer 1 is a linear urethane polymer having a gelling group at the end of the main chain.
In detail, the polymer 1 contains the following group (G-1) which is an example of the group represented by the formula (G) (when n ^G is 1) at the end of the main chain.
The following group (G-1) is a reaction product of eicosylamine (C ₂₀ H ₄₁ NH ₂ ), which is an amphiphilic gelling agent having an active hydrogen group, and an isocyanate group in HMDI.

(Synthesis of Polymers 2 to 9 (terminal, with photopolymerizable group))
Polymers 2 to 9 (terminal, photopolymerizable, all of which are linear polymers, similarly to the synthesis of the polymer 1 except that the type of the specific gelling agent as the end capping agent is changed as shown in Table 1 Group) was synthesized.
Each of Polymers 2 to 9 had a weight average molecular weight (Mw) of 8000 and an acid value of 0.70 mmol / g.

In the classification of raw materials in Tables 1 and 2, HG means hydrogelator and AMG means amphiphilic gelling agent.
The specific gelling agents in Tables 1 and 2 are as follows.
C20 H ₄₁ NH ₂ , C ₁₈ H ₃₇ NH ₂ , C ₁₆ H ₃₃ NH ₂ , and C 8 H ₁₇ NH ₂ are eicosylamine (C ₂₀ H ₄₁ NH ₂ ), octadecylamine (C ₁₈ H ₃₇ NH ₂ ), hexadecylamine (C ₁₆ H ₃₃ NH ₂ ), and octylamine, respectively. (C ₈ H ₁₇ NH ₂ ) is meant. These compounds are all amphiphilic gelling agents having an active hydrogen group.

G0402, N0949, and S0946 are all polysaccharides which are aminoethyl glycosides manufactured by Tokyo Chemical Industry Co., Ltd., and their structures are as follows. These compounds are all hydrogelators having an active hydrogen group.
In these examples using polysaccharides that are aminoethyl glycosides, the primary amino group in the polysaccharide that is aminoethyl glycoside and the isocyanate group of HMDI react with each other, and R in formula (G) ^{As U} , a urea group is formed. In these examples, n ^G in the formula (G) is 1 in all cases, L ^G in the formula (G) is ethylene, and R ^G in the formula (G) is a hydrogen atom from the polysaccharide. It becomes an excluded residue.

E 707 is an amphiphilic gelling agent having an active hydrogen group, specifically, Emalgen (registered trademark) E 707 manufactured by Kao Corporation, and more specifically, the carbon number of the linear alkyl group is 11 to 15 Monoalkyl polyethylene glycol (number average molecular weight 508).
In this example using E 707, the hydroxy group in E 707 and the isocyanate group of H MDI react to form a urethane group as R ^U in formula (G). In this example, n ^G in the formula (G) is 1, L ^G in the formula (G) is ethylene group, R ^G in the formula (G) is carbon number as a monovalent hydrophobic group. It becomes 11 to 15 linear alkyl groups.

F108 is a hydrogelating agent having an active hydrogen group, specifically, Pluronic (registered trademark) F108 manufactured by BASF, and more specifically, polyethylene glycol / polypropylene glycol / polyethylene glycol triblock copolymer ( The number average molecular weight is 14600). F108 is an example of the polyoxyalkylene compound represented by the above-mentioned formula (1A). In F108, R in Formula (1A) is a hydrogen atom.
In this example using F108, R ^U (urethane group) is formed by the reaction of the hydroxy group in the hydroxyethyl group of the terminal portion in F 108 with the isocyanate group, and the ethyl group in the hydroxyethyl group is L ^It becomes ^G (ethylene group), and the part except the hydroxyethyl group of the terminal part in F108 becomes ^RG . R ^G corresponds to a residue obtained by removing one hydrogen atom from the polyoxyalkylene compound represented by the formula (1) as a hydrogel forming agent.

(Synthesis of Comparative Polymers A and B)
Comparative polymers A and B, which are chain polymers, were respectively synthesized in the same manner as the synthesis of the polymer 1 except that the specific gelling agent as the end capping agent was changed to the comparison compound shown in Table 1.
Each of Comparative Polymers A and B had a weight-average molecular weight (Mw) of 8,000 and an acid value of 0.70 mmol / g.

In Tables 1 and 2, PEGME is polyethylene glycol monomethyl ether (number average molecular weight (Mn) = 4000), and IPA is isopropyl alcohol

(Synthesis of Polymer 10 (in the main chain, with a photopolymerizable group))
According to the following reaction scheme, polymer 10 (having a photopolymerizable group in the main chain) was synthesized as a specific chain polymer.
Here, "in the main chain" means that the polymer has a divalent gelling group in the main chain, and "with a photopolymerizable group" means that the polymer has a photopolymerizable group. Means

In a three-necked flask, dicyclohexylmethane-4,4'-diisocyanate (HMDI) (82.5 g), dimethylol propionic acid (DMPA) (16.9 g), tricyclodecane dimethanol (compound (2-5)) (2 .9 g), bisphenol A epoxy diacrylate (compound (a-21)) (77.0 g), 1,12-as a specific gelling agent (specifically, an amphiphilic gelling agent having an active hydrogen group) Dodecyl diamine (H ₂ N (CH ₂ ) ₁₂ NH ₂ ) (0.3 g) and ethyl acetate (102.3 g) were charged and heated to 70 ° C. Thereto, 0.2 g of U-600 was added and stirred at 70 ° C. for 5 hours.
Then, thereto was added isopropyl alcohol (IPA) (80 g) as an end capping agent and ethyl acetate (110 g), and the mixture was stirred at 70 ° C. for 3 hours. After stirring for 3 hours, the reaction solution was allowed to cool to room temperature and then adjusted in concentration with ethyl acetate to obtain a 30% by mass solution of polymer 9 (the solvent was ethyl acetate).
The weight average molecular weight (Mw) of the polymer 9 was 8000, and the acid value was 0.70 mmol / g.

In Table 1 and Table 2, H2N- (CH2) 12- NH2 is a 1,12-dodecyl diamine _{_{_{(H 2 N (CH 2)}}} 12 NH 2).

The polymer 10 contains the following group (G-10) which is an example of a group represented by the formula (G).
The following group (G-10) is an amphiphilic gelling agent having an active hydrogen group: 1,12-dodecyldiamine (H ₂ N (CH ₂ ) ₁₂ NH ₂ ) and an isocyanate group in HMDI It is a reactant.

(Synthesis of Polymers 11 to 16 (in the main chain, with a photopolymerizable group))
In the same manner as in the synthesis of the polymer 10 except that the type of the specific gelling agent was changed as shown in Table 1, polymers 11 to 16 which were all linear polymers were synthesized.
All of the polymers 11 to 16 had a weight average molecular weight (Mw) of 8,000 and an acid value of 0.70 mmol / g.

In Table 1, the structures of gel-01 to gel-06 are as follows, and the melting point and the molecular weight are as shown in Table 1.

Each of gel-01 to gel-06 was synthesized as follows.
Synthesis of gel-01: 20 g of 3-amino-1-propanol was dissolved in 300 mL of acetonitrile, and stirred at 0 ° C. Thereto, 26.8 g of dodecanedioic acid dichloride was dropped and stirred at 0 ° C. for 1 hour. The resulting reaction solution was poured into 300 mL of water, and hydrochloric acid was added thereto to adjust the pH to 3 or less, and then the precipitated solid was collected by filtration. The solid was washed with 300 mL water and dried at 60 ° C. for 6 hours. Thus, the desired product gel-01 was obtained.
Synthesis of gel-02: gel-02 was obtained in the same manner as in the synthesis example of gel-01 except that 3-amino-1-propanol was changed to DL-1-amino-2-propanol.
Synthesis of gel-03: In 200 mL of THF, 23 g of hexamethylenediamine and 11.4 g of ε-caprolactone were dissolved, and allowed to react for 2 hours under heating and reflux conditions. The resulting reaction solution was poured into 300 mL of water, and hydrochloric acid was added thereto to adjust the pH to 3 or less, and then the precipitated solid was collected by filtration. The solid was washed with 100 mL water and dried at 60 ° C. for 6 hours. From the above, gel-03, which is the desired product, was obtained.
Synthesis of gel-04: gel-04 was obtained in the same manner as in the synthesis example of gel-03, except that hexamethylenediamine was changed to 40 g of 1,12-dodecanediamine.
Synthesis of gel-05: gel-05 was prepared in the same manner as gel-03 except that 40 g of hexamethylenediamine and 40 g of ε-caprolactone were substituted for hexamethylenediamine and 1,12-dodecanediamine, respectively. Obtained.
-Synthesis of gel-06: In the synthesis example of gel-03, gel was similarly changed except that hexamethylene diamine was changed to 40 g of 1,12-dodecane diamine and ε-caprolactone to 8.4 g of β-butyrolactone, respectively. I got -06.

(Polymer 17)
As the polymer 17, a methacrylic polymer having a monovalent gelling group in a side chain was synthesized. Details are shown below.
In a three-necked flask, 1-methoxy-2-propanol (11.3 g) was charged, and stirred at 75 ° C. for 30 minutes under a nitrogen stream of 10 mL / min. Here, Karenz (registered trademark) MOI (manufactured by Showa Denko, 2-methacryloyloxyethyl isocyanate) (1.13 g), methyl methacrylate (10.67 g), methacrylic acid (0.90 g), V-601 (Wako Pure Chemical Industries, Ltd.) A mixed solution of dimethyl 2,2'-azobis (2-methylpropionic acid) (0.14 g) and 1-methoxy-2-propanol (11.3 g) manufactured by Yakuhin Kogyo Co., Ltd. was added dropwise over 2 hours. After completion of the dropwise addition, eicosylamine (2.29 g), which is an amphiphilic gelling agent having an active hydrogen group, was added, and the mixture was further stirred at 75 ° C. for 2 hours. The obtained reaction solution was allowed to cool to room temperature and then poured into a mixture of 200 mL of water / 20 mL of acetone. The precipitated powder was collected by filtration and dried in an oven at 60 ° C. for 6 hours. Ethyl acetate was added to the obtained powder to adjust the concentration, whereby a 30% by mass solution of Polymer 17 (the solvent was ethyl acetate) was obtained.
The weight average molecular weight (Mw) of the polymer 17 was 20000, and the acid value was 0.70 mmol / g.

(Synthesis of Polymer 101 (terminal, no photopolymerizable group))
The following polymer 101 (terminal, no photopolymerizable group) was synthesized as a specific chain polymer according to the following reaction scheme.
Here, "end" means that the polymer has a monovalent gelling group at the end of the main chain, and "no photopolymerizable group" means that the polymer does not have a photopolymerizable group. Means

In a three-necked flask, dicyclohexylmethane-4,4'-diisocyanate (HMDI) (41.2 g), dimethylol propionic acid (DMPA) (6.4 g), tricyclodecane dimethanol (compound (2-5)) (20 2 g) and ethyl acetate (67.7 g) were charged and heated to 70.degree. Thereto, 0.14 g of U-600 was added and stirred at 70 ° C. for 5 hours.
Next, eicosylamine (C ₂₀ H ₄₁ NH ₂ ) (0.2 g) as a specific gelling agent as an end capping agent and ethyl acetate (42.9 g) are added thereto, and 70 Stir at C for 3 hours. After stirring for 3 hours, the reaction solution was allowed to cool to room temperature, and then concentration adjustment was performed with ethyl acetate to obtain a 30% by mass solution of polymer 101 (solvent: ethyl acetate).
The weight average molecular weight (Mw) of the polymer 101 was 8000, and the acid value was 0.70 mmol / g.
The polymer 101 contains the group (G-1) as in the polymer 1.

(Synthesis of Polymer 102 to Polymer 104 (terminal, no photopolymerizable group))
In the same manner as in the synthesis of the polymer 101 except that the type of the specific gelling agent as the end capping agent was changed as shown in Table 2, polymers 102 to 104 as chain polymers were synthesized.
Each of the polymers 102 to 104 had a weight average molecular weight (Mw) of 8000 and an acid value of 0.70 mmol / g.

(Synthesis of Comparative Polymers C and D)
Comparative polymers C and D, which are chain polymers, were respectively synthesized in the same manner as the synthesis of the polymer 101 except that the specific gelling agent as the end capping agent was changed to the comparison compound shown in Table 2.
Each of Comparative Polymers C and D had a weight average molecular weight (Mw) of 8000 and an acid value of 0.70 mmol / g.

(Synthesis of polymer 105 (in the main chain, no photopolymerizable group))
According to the following reaction scheme, a polymer 105 (in the main chain, without a photopolymerizable group) was synthesized as a specific chain polymer.

In a three-necked flask, dicyclohexylmethane-4,4'-diisocyanate (HMDI) (41.2 g), dimethylol propionic acid (DMPA) (6.4 g), tricyclodecane dimethanol (compound (2-5)) (20 .2 g), eicosylamine (C ₂₀ H ₄₁ NH ₂ ) (0.2 g) as a specific gelling agent, and ethyl acetate (67.7 g) were charged and heated to 70 ° C. Thereto, 0.14 g of U-600 was added and stirred at 70 ° C. for 5 hours.
Then, thereto was added isopropyl alcohol (IPA) (10 g) as an end capping agent and ethyl acetate (32.9 g), and the mixture was stirred at 70 ° C. for 3 hours. After stirring for 3 hours, the reaction solution was allowed to cool to room temperature and then adjusted in concentration with ethyl acetate to obtain a 30% by mass solution of polymer 105 (the solvent was ethyl acetate).
The weight average molecular weight (Mw) of the polymer 105 was 8000, and the acid value was 0.70 mmol / g.
The polymer 105, like the polymer 10, contains a group (G-10).

(Synthesis of polymer 106 (in the main chain, no photopolymerizable group))
A polymer 106 was synthesized in the same manner as the synthesis of the polymer 105 except that the type of the specific gelling agent was changed as shown in Table 2.
The polymer 106 had a weight average molecular weight (Mw) of 8,000 and an acid value of 0.70 mmol / g.

Example 1 (Photocurable Ink)
<Preparation of water dispersion>
-Preparation of oil phase components-
Mixed solution of ethyl acetate and ethanol (ethyl acetate: ethanol (mass ratio) = 10: 1),
30% by weight solution of polymer 1 (53 parts as amount of polymer 1),
A photopolymerizable compound SR833S (22 parts; hereinafter, also referred to as “S833”) manufactured by Sartmar,
A photopolymerizable compound SR399E (22 parts; hereinafter, also referred to as “S399”) manufactured by Sartmar,
A photopolymerization initiator IRGACURE (registered trademark) 819 (2.5 parts; hereinafter, also referred to as “IRG 819”) manufactured by BASF,
2-isopropylthioxanthone (0.5 part; hereinafter, also referred to as “ITX”) manufactured by Tokyo Chemical Industry Co., Ltd. as a sensitizer
Were mixed and stirred for 15 minutes to obtain 44 g of an oil phase component having a solid content of 36% by mass.

S833 is a bifunctional photopolymerizable monomer having a cyclic structure, and specifically, it is tricyclodecanedimethanol diacrylate (molecular weight 304).
S399 is a pentafunctional photopolymerizable monomer having no cyclic structure, and specifically, is dipentaerythritol pentaacrylate (molecular weight 525).
IRG 819 is an acyl phosphine oxide type photoinitiator, specifically, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide.

-Preparation of water phase components-
An aqueous phase component was prepared by mixing distilled water (45 g) with sodium hydroxide as a neutralizing agent and stirring for 15 minutes.
The amount of sodium hydroxide used as the neutralizing agent was adjusted so that the degree of neutralization of the carboxy group in the produced particles was 90%.
The specific amount of sodium hydroxide was determined by the following formula.
Amount of sodium hydroxide (g) = total amount of oil phase component (g) × (solid content concentration of oil phase component (mass%) / 100) × (content of polymer 1 relative to total solid content of oil phase component (mass) %) / 100) × acid number of polymer 1 (mmol / g) × 0.9 × molecular weight of sodium hydroxide (g / mol) / 1000

The oil phase component and the water phase component were mixed, and the resulting mixture was emulsified at 25 ° C. using a homogenizer at 18,000 rpm for 10 minutes to obtain an emulsion. The resulting emulsion was added to distilled water (25 g) and the resulting liquid was stirred at room temperature for 30 minutes. Next, the liquid was heated to 50 ° C. and stirred at 50 ° C. for 6 hours to distill off ethyl acetate and ethanol from the liquid.
The liquid from which ethyl acetate and ethanol had been distilled off was further stirred at 50 ° C. for 24 hours to form specific particles in the liquid.
Next, an aqueous dispersion of specific particles was obtained by diluting the liquid containing the specific particles with distilled water so that the solid content is 20% by mass.

<Preparation of Photocurable Ink>
Each component of the following composition was mixed to prepare a photocurable ink.
-Composition of photocurable ink-
The above aqueous dispersion: 82 parts Pigment dispersion (Pro-jet Cyan APD 1000 (manufactured by FUJIFILM Imaging Colorants), pigment concentration: 14% by mass) 13 parts fluorosurfactant (manufactured by DuPont, Capstone FS-31) , Solid content 25% by mass) ... 0.3 parts · 2-methylpropanediol ... 4.7 parts

<Evaluation>
The following evaluation was performed using the photocurable ink obtained above.
The results are shown in Table 1.

(Scratch resistance of cured film)
By coating the above-mentioned photocurable ink stored on the substrate for one day or less at room temperature after preparation, a coating film with a thickness of 12 μm was formed on the above-mentioned substrate.
As a base material, CORREX which is a polypropylene (PP) substrate made by DUROplastic was used.
Moreover, the said application is No. 1 of the K hand coater made by RK PRINT COAT INSTRUMENTS. It carried out using 2 bars.

Next, the coated film was heated at 60 ° C. for 3 minutes to be dried.
The coating film after drying was irradiated with ultraviolet light (UV) to cure the coating film and obtain a cured film.
For ultraviolet (UV) irradiation, an experimental UV mini-conveyor CSOT equipped with an ozone-less metal halide lamp MAN250L as an exposure light source, a conveyor speed of 35 m / min, and an exposure intensity of 1.0 W / cm ² Yuasa Power Supply) was used. The UV irradiation was performed at an exposure energy of 1000 mJ / cm ² .

The scratch test of the following conditions was implemented with respect to the cured film formed above.

-Conditions of scratch test-
・ Device ... Reciprocation abrasion tester "TYPE30S" made by Haydn
-Scratching needle: SUS (stainless steel) scratching needle having a radius of curvature of 1.0 mm at the tip-Weight: 2 conditions of 100 g and 200 g-Scratching speed: 3000 mm / min.
・ Number of scratches ... 5 round trips

After the scratch test, the surface of the cured film was visually observed, and the scratch resistance of the cured film was evaluated according to the following evaluation criteria.
In the following evaluation criteria, A is the one with the best scratch resistance of the cured film.

-Evaluation criteria for scratch resistance of cured film-
A: After 5 reciprocations, no scratch marks were observed on the cured film under any of the conditions of 100 g load and 200 g load.
B: After 5 reciprocations, no scratch marks were found in the cured film under the condition of a load of 100 g, but a slight scratch mark was observed in the cured film under the condition of a load of 200 g.
C: After 5 reciprocations, a slight scratch was observed on the cured film under a load of 100 g.
D: After 5 cycles, a scratch was clearly observed on the cured film under a load of 100 g.

(Fineness of image)
The substrate is heated to 60 ° C. by a print heater, and the photocurable ink is discharged from the head of the ink jet printer to the heated substrate, and the character image shown in FIG. 1 is 3 points, 5 points , 7 points, and 10 points in each size.

The character image shown in FIG. 1 of each size thus formed was observed with a kraft loupe (manufactured by Etsumi Co., Ltd.) at a magnification of 10 times. Based on the observed results, the definition of the image was evaluated according to the following evaluation criteria. In the following evaluation criteria, A is the one with the highest definition of the image.

-Evaluation criteria for image definition-
A: The character image shown in FIG. 1 with a size of 5 points was formed without crushing and bleeding.
B: A character image shown in FIG. 1 having a size of 7 points was formed without crushing and bleeding (except in the case of A).
C: A character image shown in FIG. 1 having a size of 10 points was formed without crushing and bleeding (except in the case corresponding to A or B).
D: The character image shown in FIG. 1 with a size of 10 points was crushed or dusted.

[Examples 2 to 17] (Photocurable Ink)
The same operation as in Example 1 was performed except that Polymer 1 was changed to each polymer shown in Table 1.
The results are shown in Table 1.

[Comparative Examples 1 and 2] (Photocurable Ink)
The same operation as in Example 1 was carried out except that Polymer 1 was changed to each comparative polymer shown in Table 1.
The results are shown in Table 1.

As shown in Table 1, in Examples 1 to 17 using a photocurable ink containing water and particles containing a polymer having a gelling group (that is, specific particles), the polymer in the particles is The scratch resistance of the image and the definition of the image were excellent as compared with Comparative Examples 1 and 2 having the comparative group instead of the gelling group.

From the comparison of Examples 1 to 3 and 5 to 9 with Examples 10 to 16, when the gelling group is a monovalent group (ie, when n ^G in the formula (G) is 1) In Examples 1 to 3 and 5 to 9, it can be seen that the scratch resistance of the image and the definition of the image are further improved.

From the comparison of Examples 1 to 3 and 5 to 9 and Example 17, when the gelling group is disposed at the end of the main chain of the polymer (Examples 1 to 3 and 5 to 9), It can be seen that the scratch resistance of the image and the definition of the image are further improved.

From the results of Examples 5 to 8, when the hydrogel forming agent (HG) having an active hydrogen group is used to form a gelling group, the group corresponding to R ^G in the formula (G) is a residue of polysaccharides. In the case of the base (Examples 5 to 7), it is understood that the scratch resistance of the image and the definition of the image are further improved.

From the results of Examples 1 to 4 and 9, when the amphiphilic gelling agent (AMG) having an active hydrogen group is used to form the gelling group, the hydrophobicity corresponding to R ^G in the formula (G) When the carbon number of the sex group is 10 or more (Examples 1 to 3 and 9), it is understood that the scratch resistance of the image and the definition of the image are further improved.
Above all, when the carbon number of the hydrophobic group corresponding to R ^G in the formula (G) is 16 or more (Examples 1 to 3), the scratch resistance of the image and the definition of the image are particularly improved. Recognize.

Using the aqueous dispersion of specific particles in each of Examples 1 to 17 described above, the volume average dispersed particle size of the specific particles was measured.
As a result, in any of the examples, the volume average dispersed particle diameter of the specific particles was in the range of 0.15 μm to 0.25 μm.

Example 101 (Thermosetting Ink)
Preparation of Thermosetting Ink
In preparation of the ink, S833, S399, IRG819, and ITX a, 60 ℃, 2.67kPa (20torr) Trixene TM BI7982 ( thermally polymerizable monomer of propylene glycol monomethyl ether was distilled off under reduced pressure under the conditions of; blocked isocyanate; Baxenden Chemicals (Hereinafter referred to as “BI 7982”; the amount is as shown in Table 2; molecular weight 793), and in the same manner as Example 1 except that Polymer 1 is changed to Polymer 101 of the same amount, A thermosetting ink was prepared.

<Evaluation>
The following evaluation was performed using the thermosetting ink obtained above.
The results are shown in Table 2.

(Scratch resistance of cured film)
For evaluation of scratch resistance of the cured film, the coated film is dried by heating at 60 ° C. for 3 minutes, and the dried coated film is irradiated with ultraviolet light (UV), and the coated film is heated for 5 minutes in an oven at 120 ° C. The evaluation was conducted in the same manner as in the evaluation of the scratch resistance of the cured film in Example 1 except that the operation was changed to the heating operation.

(Fineness of image)
The definition of the image was carried out in the same manner as the evaluation of the definition of the image in Example 1.

[Examples 102, 104, 105 and 106] (Thermosetting Ink)
The same operation as in Example 101 was performed except that the polymer 101 was changed to the polymer shown in Table 2.
The results are shown in Table 2.

Example 103 (Thermosetting Ink)
The BI7982, EPICLON ^TM 840 is a thermally polymerizable monomer having an epoxy group (DIC Corporation; hereinafter referred to as "EP840"; the amount is as shown in Table 2; molecular weight 340) is a and the thermal curing accelerator 2-methylimidazole The same operation as in Example 102 was performed except that the amount was changed to “2 MI” (hereinafter, the amount is also shown in Table 2).
The results are shown in Table 2.

[Comparative Examples 101 and 102] (Thermosetting ink)
The same operation as in Example 101 was performed except that the polymer 101 was changed to a comparative polymer shown in Table 2.
The results are shown in Table 2.

As shown in Table 2, the same results as in Examples 1 to 17 for the photocurable ink were obtained in Examples 101 to 106 for the thermosetting ink.

Using the aqueous dispersion of specific particles in each of Examples 101 to 106 described above, the volume average dispersed particle size of the specific particles was measured.
As a result, in any of the examples, the volume average dispersed particle diameter of the specific particles was in the range of 0.15 μm to 0.25 μm.

Example 201 (Photocurable Ink Containing MC)
<Preparation of Water Dispersion of Microcapsule (MC)>
A microcapsule (MC) comprising a shell comprising a urethane polymer which is a specific crosslinked polymer having a three-dimensional crosslinked structure, and a core containing a photopolymerizable monomer, a photopolymerization initiator, and a sensitizer as follows: Water dispersion was prepared.
In this example, microcapsules (MC) correspond to specific particles.

-Preparation of oil phase components-
With ethyl acetate,
Takenate (registered trademark) D-110N (43 parts as the amount of solid trifunctional isocyanate compound; manufactured by Mitsui Chemicals, Inc .; hereinafter, this solid is also referred to as “D110”),
A solution of the following NCO1 (10 parts as an amount of NCO1 which is a solid content),
S833 (20.5 parts) described above, which is a photopolymerizable monomer,
S399 (22 parts) as described above which is a photopolymerizable monomer,
The aforementioned IRG 819 (2.5 parts), which is a photopolymerization initiator,
With the above-mentioned ITX (0.5 part) which is a sensitizer,
Were mixed and stirred for 15 minutes to obtain 45.7 g of an oil phase component having a solid content of 30% by mass.

Takenate D-110N is a 75% by mass ethyl acetate solution of an adduct of trimethylolpropane (TMP) and m-xylylene diisocyanate (XDI) (trifunctional isocyanate compound “D110”).

NCO1 is an isocyanate compound having a carboxy group introduced, and specifically, an adduct of 2,2-bis (hydroxymethyl) butyric acid (DMBA) and IPDI (DMBA / IPDI = 1/3 (molar ratio)) It is. The acid value of NCO1 is 1.2 mmol / g.
The above solution of NCO1 is a 35% by weight solution of NCO1 in ethyl acetate.
A solution of NCO 1 is added to a three-necked flask, 18 g of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 82 g of isophorone diisocyanate (IPDI) and 186 g of ethyl acetate (AcOEt), heated to 50 ° C. It was prepared by adding 0.3 g of U-600 and reacting for 3 hours.

-Preparation of water phase components-
Distilled water (43.1 g), sodium hydroxide as a neutralizing agent, and eicosylamine (C ₂₀ H ₄₁ NH ₂ ) as a specific gelling agent are mixed, and water is stirred for 15 minutes. The phase components were prepared.
Wherein the amount of eicosyl amine _(C _{20 H} 41 NH ₂₎ was set to 1.5 parts relative to D110 of 43 parts of the foregoing.
The amount of sodium hydroxide used as the neutralizing agent was adjusted so that the degree of neutralization of the carboxy group in the manufactured MC was 90%.
The specific amount of sodium hydroxide was determined by the following formula.
Amount of sodium hydroxide (g) = total amount of oil phase component (g) × (solid content concentration of oil phase component (mass%) / 100) × (content of NCO 1 with respect to total solid content of oil phase component (mass%) ) / 100) × NCO 1 acid value (mmol / g) × 0.9 × molecular weight of sodium hydroxide (g / mol) / 1000

The oil phase component and the water phase component were mixed, and the obtained mixture was emulsified at room temperature for 10 minutes at 12000 rpm using a homogenizer to obtain an emulsion. The obtained emulsion was added to distilled water (15.3 g), and the obtained liquid was heated to 50 ° C. and stirred at 50 ° C. for 5 hours to evaporate ethyl acetate from the liquid. The remaining liquid was diluted with distilled water so as to have a solid content of 20% by mass, to obtain a water dispersion of microcapsules.

The polymer which is the shell of this microcapsule is a urethane polymer having a three-dimensional crosslinked structure formed by the reaction of D110 which is a trifunctional isocyanate compound, and NCO1 which is an isocyanate compound having a carboxy group introduced. The terminal of this urethane polymer is sealed by the reaction between eicosylamine, which is a specific gelling agent as an end-capping agent, and an isocyanate group.
The polymer that is the shell of this microcapsule is
Urethane group originally contained in NCO1,
Urethane group originally contained in D110, and
It has a urea group formed by the reaction of an isocyanate group in D110 or NCO1, an isocyanate group in D110 or NCO1, and water.

<Evaluation>
The same evaluation as that performed in Example 1 was performed using the obtained photocurable ink.
The results are shown in Table 3.

As shown in Table 3, it was also confirmed that Example 201 related to a photocurable ink containing MC as specific particles has an excellent effect of scratch resistance of an image and definition of an image.

From the comparison between Example 201 (Table 3) and Example 1 (Table 1) described above, in Example 1 in which the chain polymer (Polymer 1) is contained as the specific polymer, the third polymer which is the shell of MC as the specific polymer It is understood that the scratch resistance of the image and the fineness of the image are superior to Example 201 containing the original crosslinked polymer.

The volume average dispersed particle size of MC was measured using the aqueous dispersion of MC in Example 201 described above, and the volume average dispersed particle size of MC was in the range of 0.15 μm to 0.25 μm.

[Example 301] (Thermosetting ink containing MC)
Preparation of Thermosetting Ink
In the following manner, an aqueous dispersion of microcapsules (MC) containing a shell composed of a urethane polymer which is a specific crosslinked polymer having a three-dimensional crosslinked structure, and a core containing a thermally polymerizable monomer was prepared.
In this example, microcapsules (MC) correspond to specific particles.

Specifically, a thermosetting resin was prepared in the same manner as in the preparation of the photocurable ink in Example 201 except that S833, S399, IRG 819, and ITX were changed to BI7982 (the amounts are as shown in Table 4). An ink was prepared.
In the thermosetting ink, the structure of the polymer forming the shell of MC is similar to the structure of the polymer forming the shell of MC in Example 201.

<Evaluation>
Evaluation similar to Example 101 regarding thermosetting ink was performed using the thermosetting ink obtained above.
The results are shown in Table 4.

As shown in Table 4, the same results as Example 201 for the MC-containing photocurable ink were obtained also in Example 301 for the MC-containing thermosetting ink.

From the comparison between this Example 301 (Table 4) and the above-mentioned Example 101 (Table 2), in Example 101 including the chain polymer (polymer 101) as the specific polymer, the third order being the shell of MC as the specific polymer It is understood that the scratch resistance of the image and the fineness of the image are superior to those of Example 301 containing the original crosslinked polymer.

When the volume average dispersed particle size of MC was measured using the aqueous dispersion of MC in Example 301 described above, the volume average dispersed particle size of MC was in the range of 0.15 μm to 0.25 μm.

The disclosure of Japanese Patent Application 2017-183868, filed on September 25, 2017, is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are as specific and distinct as when individual documents, patent applications, and technical standards are incorporated by reference. Hereby incorporated by reference.

Claims

water and,
Particles comprising a polymer having a gelling group which is a urethane polymer, a urea polymer or a (meth) acrylic polymer and which is a reaction product of a gelling agent having an active hydrogen group and an isocyanate group;
An ink composition containing
The ink composition according to claim 1, wherein the gelling group is a group represented by the following formula (G).

In formula (G), n G represents 1 or 2, R U represents a urethane group, a urea group, a thiourethane group, or a thiourea group, and L G represents a single bond or a divalent linking group. , * Represents a bonding position.
In the formula (G), R G is a polysaccharide, a protein, an acrylic resin, a vinyl resin, or a hydrogelator which is a polyoxyalkylene compound represented by the formula (1) when n G is 1. It represents a residue from which one hydrogen atom has been removed, or a monovalent hydrophobic group.
In formula (G), when n G is 2, R G represents a residue obtained by removing two hydrogen atoms from the hydrogelator, or represents a divalent hydrophobic group.
In formula (1), n and m each independently represent an integer of 2 or more, p represents an integer of 0 or more, L represents an alkylene group having 3 or more carbon atoms, and R is a hydrogen atom , An alkyl group or an aryl group.
The hydrogel agent is the polysaccharide or a polyoxyalkylene compound represented by the formula (1),
The monovalent hydrophobic group is a linear alkyl group having 10 or more carbon atoms,
The ink composition according to claim 2, wherein the divalent hydrophobic group is a linear alkylene group having 10 or more carbon atoms.
The hydrogelator is the polysaccharide,
The monovalent hydrophobic group is a linear alkyl group having 16 or more carbon atoms,
The ink composition according to claim 2 or 3, wherein the divalent hydrophobic group is a linear alkylene group having 16 or more carbon atoms.
5. The ink composition according to any one of claims 2 to 4, wherein the R U in the formula (G) is a urea group.
The ink composition according to any one of claims 1 to 5, wherein the gelling group is a monovalent group.
The polymer is a linear polymer,
The ink composition according to claim 6, wherein the gelling group is disposed at the end of the main chain of the linear polymer.
The ink composition according to any one of claims 1 to 7, wherein the particles contain a polymerizable monomer.
The ink composition according to any one of claims 1 to 8, wherein the polymer has a polymerizable group.
The ink composition according to any one of claims 1 to 9, which is used as an inkjet ink.
A method of producing the ink composition according to any one of claims 1 to 10, wherein
A method for producing an ink composition, comprising the steps of forming the particles by mixing and emulsifying an organic phase and an oil phase component containing the polymer, and an aqueous phase component containing water.
Forming an ink film by applying the ink composition according to any one of claims 1 to 10 on a substrate;
Heating the ink film;
An image forming method including: