JP2014177098A - Image formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image formation method for forming an image that is superior in image scratch resistance and has excellent drape properties.SOLUTION: A method comprises an ink application step for applying an inkjet ink composition at least comprising polymer particles, water-soluble photocurable polymers, and water, to a recording base material that is an aggregate of non-absorptive or low-absorptive fiber materials, by inkjet method.

Description

  The present invention relates to an image forming method using an inkjet method.

  Conventionally, analog printing such as screen printing has been performed as a method for forming a design on a fiber. However, in recent years, in order to meet demands for small lots, multiple varieties, short delivery times, or cost reductions, an ink jet method is used. Digital printing using the printer is under consideration.

Since fibers with such a design are widely used in daily products such as clothing and masks, the durability of the image is one of the important performances in terms of quality.
In order to record an image on a fiber by an inkjet method, as one of the methods for imparting durability to the formed image, a technique of incorporating an aqueous resin emulsion, that is, polymer particles as a fixing agent in an inkjet ink has been attempted. (For example, refer to Patent Document 1).

  In addition, as an attempt to improve the durability of images formed on fibers, a technique has been proposed in which inkjet ink contains a water-soluble fixing material having a crosslinkable functional group and is crosslinked and fixed by heating on the fiber. (For example, refer to Patent Document 2). Furthermore, in order to improve the solvent resistance of an image formed by the ink jet method and the fixability to a recording medium, studies using a photocurable polymer have been made (for example, see Patent Document 3).

  In addition to the above, for example, a composition of an inkjet ink containing a wetting agent such as a resin emulsion or glycerin together with a pigment or the like is disclosed, and it is said that an effect of promoting fixing to paper is obtained by using the resin emulsion ( For example, see Patent Document 4). Further, although there is a document disclosing an ink composition containing a compound having a maleimide structure (see, for example, Patent Documents 5 to 6), a composition for maintaining drape is not shown.

JP 2006-249203 A JP 2012-251062 A JP 2013-6968 A JP 2012-51357 A JP 2012-1639 A JP2012-144645A

  However, among the above-described conventional techniques, merely containing polymer particles as an image fixing agent can be expected to improve the abrasion resistance to some extent as compared with the case where polymer particles are not included, but is generally used for ink jet recording. For example, compared to an image formed on a surface such as a paper medium, the effect of improving the durability of an image formed on a fiber is not necessarily sufficient.

In addition, the technique of fixing an image on a fiber using a fixing material having a crosslinkable functional group does not always provide sufficient durability of the image, but also heats the image to improve durability. Therefore, there is a concern that the texture and drape feeling of the fiber material may be impaired. Furthermore, since the fixing agent has thermal reactivity, the storage stability of the ink itself is also lowered.
On the other hand, the ink containing the photocurable polymer as described above contributes to improvement of the fixability, but the formed image becomes too hard, so that the texture and drape of the image are only deteriorated. However, there is a problem that the durability of the image is impaired.

  In particular, when forming an ink image using a non-absorbent or low-absorbent synthetic fiber such as polypropylene as a recording medium, the fiber itself does not absorb ink, so the ink is difficult to fix and the image is resistant to abrasion. It is difficult to ensure. On the other hand, such non-woven fabrics are used in sanitary products such as diapers, so even if the durability of the image is obtained, the touch and wearing feeling may be impaired due to the influence of the image being too hard, or the texture may be poor. It is not desirable to be.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an image forming method in which an image having excellent image scratch resistance and good drape properties is formed. Is an issue.

  “Drapability” in the present invention refers to the flexibility and flexibility of a substrate on which an image is formed. The flexibility and flexibility that are maintained when an image is formed on a substrate having flexibility and flexibility. It is evaluated by the degree.

  In the present invention, when a water-soluble photocurable polymer that does not belong to a so-called thickener is used as an ink component, not only the resistance of the film to an external force is increased, but also the stability and ejection properties of the ink are improved. It can be expected to increase the viscosity of the ink while maintaining it, making it easy to form images on non-woven fabrics and other fiber materials, and the formed images have high film strength but also drape, so image durability is good. It has been achieved based on such knowledge.

Specific means for achieving the above-described problems are as follows.
<1> An inkjet ink composition containing at least polymer particles, a water-soluble photocurable polymer, and water is formed on a recording substrate that is an aggregate of non-absorbable or low-absorbent fiber materials by an inkjet method. An image forming method including an ink application step of applying.
<2> The image forming method according to <1>, wherein the inkjet ink composition further contains a compound selected from the group consisting of a polyhydric alcohol compound, an amide compound, and an amine compound.
<3> The image forming method according to <1> or <2>, wherein the photocurable polymer has a partial structure represented by the following general formula (1).

In General Formula (1), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R ^a and R ^b is an alkyl group having 1 to 4 carbon atoms. Represents. R ^a and R ^b may be bonded to each other to form a 4- to 6-membered alicyclic structure. “*” Represents a binding site with a main chain or a side chain in the polymer.
<4> The image forming method according to any one of <1> to <3>, wherein the photocurable polymer has a repeating unit represented by the following general formula (2).

In General Formula (2), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R ^a and R ^b is an alkyl group having 1 to 4 carbon atoms. Represents. R ^a and R ^b may be bonded to each other to form a 4- to 6-membered alicyclic structure. R ^c represents a hydrogen atom or a methyl group. Z represents a single bond, —COO — ^** or —CONR ^d — ^** , R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and “**” represents a bonding position with X. . X represents an alkylene group or an aralkylene group.

<5> The image forming method according to any one of <1> to <4>, wherein a glass transition temperature (Tg) of the polymer particles is −40 ° C. to 60 ° C.
<6> The image forming method according to any one of <1> to <5>, wherein the polymer particles are particles containing a resin selected from the group consisting of a urethane resin, an acrylic resin, and a styrene resin. is there.
<7> The image according to any one of <2> to <6>, wherein the compound selected from the group consisting of a polyhydric alcohol compound, an amide compound, and an amine compound has a vapor pressure at 25 ° C. of less than 1 Pa. It is a forming method.
<8> The total content of the compound selected from the group consisting of a polyhydric alcohol compound, an amide compound, and an amine compound is in the range of 1% by mass to 15% by mass with respect to the total mass of the inkjet ink composition. The image forming method according to any one of <2> to <7>.
<9> The method according to any one of <1> to <8>, further including a light irradiation step of irradiating an image formed by applying the inkjet ink composition on the recording substrate in the ink application step. This is an image forming method.
<10> The ink application process is the image forming method according to any one of <1> to <9>, in which the inkjet ink composition is applied to the recording substrate with an ink droplet amount of 30 pl to 120 pl.
<11> The ratio (P / CP) of the content (P) of the polymer particles to the content (CP) of the photocurable polymer is in the range of 9.5 / 0.5 to 2/8 in mass ratio < The image forming method according to any one of 1> to <10>.

  ADVANTAGE OF THE INVENTION According to this invention, the image forming method which is excellent in the abrasion resistance of an image, and the image which has favorable drape property is formed is provided.

Hereinafter, the image forming method of the present invention will be described in detail.
According to the image forming method of the present invention, an inkjet ink composition containing at least polymer particles, a water-soluble photocurable polymer, and water is a recording that is an aggregate of non-absorbing or low-absorbing fiber materials by an inkjet method. An ink applying step for applying on the substrate is provided. In addition, the image recording method of the present invention can be configured by providing a light irradiation step for curing the inkjet ink composition applied in the ink application step, and a step of drying or dry-fixing the inkjet ink composition. Further, other steps may be provided as necessary.

2. Description of the Related Art Conventionally, it has been attempted to record an image using, as a recording medium, an aggregate of fiber materials (nonwoven fabric or the like) formed by aggregating non-ink-absorbing or low-absorbing fibers such as polypropylene and polyethylene. Since such a material has a relatively rough spatial structure, in order to record an image by applying ink droplets by the ink jet method, it is advantageous that the ink has a certain viscosity, and a method for increasing the viscosity. In general, a thickener is included in the ink. On the other hand, when a commonly used thickener is added to the ink, the stability of the ink itself is impaired, and the ink ejection property tends to be lowered. In addition, a technique for increasing the durability of an image using a monomer is also known, but with a monomer, the strength of the image can be increased, but it becomes too hard to maintain the resistance to bending and bending, and the image is not maintained. Cracks are likely to occur.
In view of the above, the present invention does not perform viscosity adjustment using a component generally referred to as a thickening agent, but contains a water-soluble and photocurable polymer component as a thickening component, thereby stabilizing the ink. In addition, while maintaining good dischargeability, the image forming property to the fiber material is ensured and the film strength of the image is increased. At this time, an image to be formed is hardened by a curing reaction of the polymer. However, since the drape property is impaired when the image becomes too hard, the use of polymer particles in combination gives more flexibility to the image.
That is, in the present invention, the composition containing polymer particles together with a water-soluble photocurable polymer provides flexibility to the image while increasing the film strength of the image, so that it is difficult for cracks to occur due to bending or bending. In addition, an image having excellent scratch resistance and good drape properties can be obtained. That is, it is possible to achieve both image scratch resistance and drape, which are mutually contradictory properties in a normal ink composition. Furthermore, the softness and suppleness of the image are imparted, so that when the image is formed, the texture (for example, feel, deformability, appearance, etc.) of the recording base material and the image formed product is also reduced. Alleviated.
The draping property and texture of the image can be further enhanced by using an ink composition further containing a compound having a vapor pressure (25 ° C.) of less than 1 Pa and hardly vaporized.

[Ink application process]
In the ink application process in the present invention, the ink-jet ink composition is applied onto a recording substrate which is an aggregate of non-absorbing or low-absorbing fiber materials by an ink-jet method. The ink-jet ink composition used in this step includes at least polymer particles, a water-soluble photocurable polymer, and water, and is configured in an aqueous system using water as a main solvent. Details of the inkjet ink will be described later.

Application of the inkjet ink to the recording substrate is performed by an inkjet method. By the ink jet method, ink is selectively applied to a desired region.
The inkjet method is not particularly limited, and is a known method, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, An acoustic ink jet system that converts an electrical signal into an acoustic beam, irradiates the ink with ink, and ejects the ink using radiation pressure, and a thermal ink jet that forms bubbles by heating the ink and uses the generated pressure (bubble jet (registered) Trademark)) method or the like.

  When ink is applied onto a recording substrate by an ink jet method, the application method may be multipass or one pass, but one pass or two passes is preferable from the viewpoint of high-speed recording. Here, one pass means that all the dots (ink droplets) to be formed in the scanning region in that direction are formed by one ejection in the direction intersecting with the conveyance direction of the recording substrate (arrangement direction of the recording elements). Recording method. In this case, an ejection head (line head in which recording elements are arranged) having a length corresponding to the width of the base material is provided in the base material width direction intersecting the transport direction of the recording base material transported during recording, Ink is ejected simultaneously in the main scanning direction from a plurality of ejection holes provided in the ejection head. This is called a so-called line method, and an image can be recorded on the entire surface of the recording substrate by scanning the recording substrate in a direction crossing the arrangement direction of the recording elements. This method does not require a transport system such as a carriage as in the shuttle method that records while scanning a short serial head in the width direction (main scanning direction) of the recording substrate. The two passes are a method of recording by forming dots to be formed in the scanning region by two ejections.

The ink jet head used in the ink application process in the present invention is not particularly limited, but for example, an ink jet head mainly used for industrial use is preferably used. The industrial inkjet head is preferably a head capable of ejecting a relatively large amount of ink droplets of 60 pL or more. Among them, the material inside the head, specifically, the material of the ink flow path is a hydrophobic composition, For example, a head made of carbon, polyimide, or the like is particularly suitable. Furthermore, a head surface (for example, the surface of a nozzle plate on which a plurality of nozzle holes are arranged) having nozzle holes from which ink is ejected is relatively hydrophilic and has low liquid repellency (not liquid-repellent treatment), For example, a head composed of a metal or a metal compound has a large amount of ink droplets, so that the ink tends to remain on the head surface. However, the ink-jet ink of the present invention is also suitable for such an ink-jet head. .
Examples of such inkjet heads are SapphireQS256 / 10, SapphireQS256 / 30, SapphireQS256 / 80, EmeraldQE256 / 30, EmelaldQE256 / 80, Galaxy256 / 30, Galaxy12ar, 80 Polaris 512/85, SG-1024 (both manufactured by FUJIFILM DIMATIX).

The amount of ink droplets applied to the recording substrate is preferably in the range of 30 pl to 120 pl. An ink droplet amount in the range of 30 pl or more and 120 pl or less means that a large amount of ink is applied to an aggregate of fibrous materials such as nonwoven fabric. In other words, when the amount of ink droplets is 30 pl or more, when recording on a nonwoven fabric or the like having a relatively rough substrate surface, it is desired even if a certain distance is secured between the substrate and the head. Easy to get images. That is, since the fibers of the recording substrate itself have poor ink absorbability, some of the applied ink droplets adhere to the fibers and remain on the fibers to form colored portions, but cannot be adhered and retained on the fibers. Since the amount of droplets is easily separated and easily enters the deep part of the material, it is preferable that the ejected inkjet ink composition has a large droplet amount of 30 pl or more so that a certain droplet size can be obtained. In this regard, when the material itself such as pulp absorbs ink and forms an image on sheet paper (plain paper, etc.) where the ink composition that has landed spreads and is fixed not only in the thickness direction of the sheet but also in the surface direction. Different from the amount of ink drops.
Further, when the ink droplet amount is 30 pl or more, it becomes easy to secure an ink region on the fiber, and the image scratch resistance is further improved. On the other hand, when the ink droplet amount is 120 pl or less, the drying property of the droplets on the surface of the substrate can be maintained, which is advantageous in preventing the occurrence of image bleeding. Among them, the ink droplet amount is more preferably in the range of 30 pL to 100 pL, and further preferably in the range of 30 pL to 90 pL.

  The ink droplet amount in the present invention may have the above-mentioned ink droplet amount by one droplet ejected from an inkjet nozzle, or before ejecting two or more droplets and landing on a recording substrate. It is only necessary to have the above-described ink droplet amount together. That is, it is sufficient that the ink droplet amount is ensured with one liquid just before landing on the recording substrate.

  The diameter of the ink droplets applied to the recording substrate (the diameter before landing) is preferably 38 μm to 61 μm, and more preferably 38 μm to 56 μm. The diameter of the ink droplet can be directly measured by droplet observation with a high speed camera (for example, Hyper Vision HPV-2A manufactured by Shimadzu Corporation).

  The viscosity (30 ° C.) of the inkjet ink is preferably 4 mPa · s to 20 mPa · s, more preferably 6 mPa · s to 16 mPa · s, from the viewpoint of stably supplying ink from the ink tank to the recording head.

  For example, the resolution per color is preferably 100 dpi (dot per inch) or more, and the ink viscosity is preferably 4 mPa · s to 20 mPa · s (30 ° C.). The resolution is preferably 200 dpi or more from the viewpoint of high image quality.

-Inkjet ink composition-
The ink-jet ink composition in the present invention is composed of a composition containing at least polymer particles, a water-soluble photocurable polymer, and water. The ink-jet ink composition of the present invention preferably contains a colorant, and further comprises components such as a pigment dispersant, a water-soluble organic solvent, a surfactant, and other additives as necessary. be able to.

(Polymer particles)
The ink-jet ink composition in the present invention contains at least one polymer particle. By containing the polymer particles, an effect of reducing the image strength obtained by containing the photocurable polymer described later can be obtained, and both resistance to scratching and flexibility (drapability) of the image can be achieved.

Examples of polymer particles include thermoplastic, thermosetting, or modified acrylic resins, epoxy resins, urethane resins, polyolefin resins, styrene resins, ether resins, amide resins, and unsaturated polyester resins. Resin, phenolic resin, silicone resin, fluorine resin, vinyl resin (eg, vinyl chloride, vinyl acetate, polyvinyl alcohol, or polyvinyl butyral), alkyd resin, ester resin (eg, phthalic acid resin, etc.), Examples thereof include particles of an amino material (eg, melamine resin, melamine formaldehyde resin, aminoalkyd cocondensation resin, urea resin, urea resin, etc.), or a copolymer or a mixture thereof.
As a polymer particle, 1 type may be used individually and 2 or more types may be used together. Further, polymer particles constituted by mixing two or more kinds of polymers or polymer particles constituted by combining two or more kinds of monomers may be used.

Among the above, as the polymer particles, urethane resin, acrylic resin, styrene resin, polyether resin, polyester resin, or polyolefin resin particles are preferable, urethane resin, acrylic resin, or styrene resin Resin particles are more preferable, and urethane resin particles are particularly preferable from the following viewpoints.
By selecting the urethane-based resin particles, the ink discharge performance is improved, and the discharge qualities during continuous discharge are further improved, and the scratch resistance of the recorded image is also improved.

The reason why the urethane resin is suitable is estimated as follows. That is,
Urethane resin is made up of urethane sites that allow strong interactions such as hydrogen bonding between polymers and non-urethane sites that have relatively weak interactions between polymers, forming an ink film. As a micro structure, it is estimated that a relatively strong interaction part and a relatively weak interaction part gather together to construct a sea-island structure, which makes polyurethane flexible. It is estimated to be. Since polyurethane is inherently flexible in this way, it is possible to use one having a high Tg, as compared to the conventional example using low Tg polymer particles, and the flexibility and strength are improved. It is presumed that an ink film (ink image) having excellent scratch resistance can be formed.
Therefore, it is particularly advantageous when a “recording substrate that is an aggregate of non-absorbent or low-absorbent fiber materials” that is difficult to obtain scratch resistance.

The polymer particles are preferably self-dispersing polymer particles having self-dispersibility. When the self-dispersing polymer particles are in a dispersed state (particularly, a dispersed state by a phase inversion emulsification method) in the absence of a surfactant, the polymer itself has a functional group (especially an acidic group or a salt thereof), which causes an aqueous medium. It means water-insoluble polymer particles which can be dispersed in the water-insoluble polymer and do not contain a free emulsifier.
The self-dispersing polymer particles are preferable from the viewpoint of ejection stability and liquid stability (particularly dispersion stability) of a system containing a pigment, and among them, self-dispersing polymer particles having a carboxyl group are more preferable.

The dispersed state means both an emulsified state (emulsion) in which a water-insoluble polymer is dispersed in a liquid state in an aqueous medium and a dispersed state (suspension) in which a water-insoluble polymer is dispersed in a solid state in an aqueous medium. Is included.
The water-insoluble polymer in the present invention is preferably a water-insoluble polymer that can be in a dispersed state in which the water-insoluble polymer is dispersed in a solid state from the viewpoint of fixability when a liquid composition is used.

  Examples of a method for preparing an emulsified or dispersed state of the self-dispersing polymer, that is, an aqueous dispersion of the self-dispersing polymer include a phase inversion emulsification method. As the phase inversion emulsification method, for example, a self-dispersing polymer is dissolved or dispersed in a solvent (for example, a hydrophilic organic solvent) and then poured into water as it is without adding a surfactant. Examples include a method of obtaining an aqueous dispersion in an emulsified or dispersed state after stirring and mixing in a state in which a salt-forming group (for example, an acidic group) of the polymer is neutralized and removing the solvent.

  The dispersion state of the self-dispersing polymer particles refers to a solution in which 30 g of a water-insoluble polymer is dissolved in 70 g of an organic solvent (for example, methyl ethyl ketone), a neutralizing agent (salt that can neutralize 100% of the salt-forming groups of the water-insoluble polymer). After mixing and stirring (equipment: stirring device with stirring blade, rotation speed 200 rpm, 30 minutes, 25 ° C.), sodium hydroxide if the generating group is anionic, acetic acid if cationic, and 200 g of water are mixed, It means a state in which even after removing the organic solvent from the mixed solution, it can be visually confirmed that the dispersion state exists stably at 25 ° C. for at least one week.

  The water-insoluble polymer means a polymer having a dissolution amount of 10 g or less when the polymer is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C., and the dissolution amount is preferable. Is 5 g or less, more preferably 1 g or less. The dissolution amount is the dissolution amount when 100% neutralized with sodium hydroxide or acetic acid according to the type of salt-forming group of the water-insoluble polymer.

  The aqueous medium is configured to include water, and may include a hydrophilic organic solvent as necessary. In the present invention, it is preferably composed of water and 0.2% by mass or less of a hydrophilic organic solvent with respect to water, and more preferably composed of water.

The main chain skeleton of the water-insoluble polymer is preferably a polyurethane.
Suitable examples of monomers constituting the condensation polymer are described in JP-A No. 2001-247787. Polyurethane is synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials. For details of the diol compound and the diisocyanate compound, reference can be made to the descriptions in paragraph numbers [0031] to [0036] of JP-A No. 2001-247787.

  As a particle | grains containing a urethane type resin, the particle | grains containing the polyurethane which has a structure represented by the following general formula (PU-1) are preferable.

In General Formula (PU-1), R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a residue of the diol compound.
Examples of the aliphatic group represented by R ₁ include a divalent group derived from isophorone diisocyanate (IPDI), hydrogenated m-xylene diisocyanate (H6XDI), hydrogenated diphenylmethane diisocyanate (H12MDI), hexamethylene diisocyanate (HDI), and the like. Is mentioned.
Examples of the aromatic group represented by R ₁ include divalent groups derived from m-xylene diisocyanate (XDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and the like.
Among these, R ₁ is preferably an aliphatic group from the viewpoint of image durability. This is presumably because by selecting a relatively soft structure, the flexibility of the ink film after the ink is fixed on the base material is improved and the image durability is increased.

The residue of the diol compound represented by R ₂ is preferably a group selected from an alkylene group, a polyether group, a polyester group, a polycarbonate group, and a polycaprolactone group, and more preferably an alkylene group, a polyether group, and a polyester. And a polycaprolactone group, particularly preferably an alkylene group having 1 to 30 carbon atoms, an alkyl ether group having 2 to 60 carbon atoms, and an alkyl ester group having 1 to 30 carbon atoms. This is presumably because by selecting a relatively soft structure, the flexibility of the ink film after the ink is fixed on the base material is improved and the image durability is increased.
M represents an integer and may be appropriately selected within a range satisfying the following molecular weight.

The polyurethane particles may be either those having a cross-linked structure therein or those having no cross-linked structure, but those having no cross-linked structure are more preferable from the viewpoint of image fixability.
As the particles of the polyurethane resin, commercially available products may be used. As examples of commercially available products, ACRYTE WBR-016U (Tg: 20 ° C.), WEM-321U (Tg: 20) manufactured by Taisei Fine Chemical Co., Ltd. ° C), WBR-2018 (Tg: 20 ° C), WBR-2000U (Tg: 45 ° C), WBR-601U (Tg: -30 ° C), PUE-1000 manufactured by Murayama Chemical Research Ltd., PUE -1020A, PUE-1370, PUE-800, Superflex 650, 860, 210 manufactured by Daiichi Kogyo Seiyaku, Neotan UE-1100 manufactured by Toagosei Co., Ltd., Yucote UX-150 manufactured by Sanyo Chemical Industries UWS-145, Barmarin UA-150, UA-368, Iupylene UXA-307, Impura manufactured by Sumika Bayer Urethane Co., Ltd. DLP-R (Tg: 21 ° C), DLN (Tg: -55 ° C), DLC-F (Tg: -42 ° C), Bihydrol (UH XP2648 (Tg: -51 ° C), Dispacol U- 53 (Tg: −58 ° C.), Permarine UA-150 (Tg: 36 ° C.) manufactured by Sanyo Chemical Co., Ltd., UW-1005-E (Tg: −30 ° C.) manufactured by Ube Industries, Ltd., UW-5101-E (Tg) : 69 ° C.).

As the polymer particles, acrylic resin particles are also suitable.
As the acrylic resin, a resin having an anionic group is preferable. Such an acrylic resin, for example, polymerizes an acrylic monomer having an anionic group (anionic group-containing acrylic monomer) and, if necessary, other monomers copolymerizable with the anionic group-containing acrylic monomer in a solvent. It is a homopolymer or copolymer obtained. As an anionic group containing acrylic monomer, the acrylic monomer which has 1 or more chosen from a carboxyl group, a sulfonic acid group, and a phosphone group is mentioned, for example. Among them, an acrylic monomer having a carboxyl group (for example, acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, etc.) is preferable, and acrylic acid or methacrylic acid is particularly preferable. preferable.

  Commercially available products may be used as the acrylic resin particles. As examples of commercially available products, Aron HD-5 manufactured by Toa Gosei Co., Ltd. (Tg: 45 ° C., acrylic type), Movinyl 742N manufactured by Nichigo Co., Ltd. (Tg: 37 ° C., acrylic).

Styrene resin particles are also suitable as the polymer particles.
Examples of the styrene resin include styrene homopolymers and copolymers of styrene and other monomers such as acrylic monomers. As an acrylic monomer, the same anionic group containing acrylic monomer as said acrylic resin is mentioned.

  Commercially available products on the market may be used as the styrene resin particles. Examples of commercially available products include John Crill 741 (Tg: 15 ° C., styrene / acrylic resin) manufactured by Johnson Polymer Co., Ltd., 775. (Tg: 37 ° C., styrene / acrylic resin), 537 (Tg: 49 ° C., styrene / acrylic resin), and 538 (Tg: 66 ° C., styrene / acrylic resin).

As molecular weight of a polymer particle, the range of 3000-300000 is preferable at a weight average molecular weight, and the range of 5000-200000 is more preferable. The weight average molecular weight is a value measured as a polystyrene equivalent value using gel permeation chromatography (GPC). The measurement conditions are as follows.
<Condition>
・ GPC: HLC-8220 GPC [manufactured by Tosoh Corporation]
Column: TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, TSKgeL SuperHZ2000 (all manufactured by Tosoh Corporation)
-Mobile phase solvent: Tetrahydrofuran-Standard sample: Standard polystyrene-Flow rate: 0.35 ml / min
-Column temperature: 40 ° C

  There is no restriction | limiting in particular in the manufacturing method of the water-insoluble polymer which comprises a polymer particle. For example, a method in which emulsion polymerization is performed in the presence of a polymerizable surfactant and a surfactant and a water-insoluble polymer are covalently bonded, and a monomer mixture containing a hydrophilic group-containing monomer and an aromatic group-containing monomer is solution-polymerized. And a method of copolymerization by a known polymerization method such as a bulk polymerization method. Among the polymerization methods, from the viewpoint of droplet ejection stability when used as an ink, a solution polymerization method is preferable, and a solution polymerization method using an organic solvent is more preferable.

The polymer particles include a polymer synthesized in an organic solvent, the polymer has a carboxyl group (preferably having an acid value of 1 to 50), and part or all of the carboxyl group of the polymer is neutralized. And is preferably prepared as a polymer dispersion having water as a continuous phase. That is, the production of the polymer particles in the present invention is preferably performed by providing a step of synthesizing a polymer in an organic solvent and a dispersion step of making an aqueous dispersion in which at least a part of the carboxyl groups of the polymer is neutralized. .
The dispersion step preferably includes the following step (1) and step (2).
Step (1): Step of stirring a mixture containing a polymer (water-insoluble polymer), an organic solvent, a neutralizing agent, and an aqueous medium Step (2): Step of removing the organic solvent from the mixture

  Step (1) is preferably a treatment in which a polymer (water-insoluble polymer) is first dissolved in an organic solvent, then a neutralizing agent and an aqueous medium are gradually added, mixed and stirred to obtain a dispersion. In this way, by adding a neutralizing agent and an aqueous medium to a water-insoluble polymer solution dissolved in an organic solvent, a self-dispersing polymer having a particle size with higher storage stability without requiring strong shearing force. Particles can be obtained. There is no restriction | limiting in particular in the stirring method of a mixture, Dispersing machines, such as a generally used mixing stirring apparatus and an ultrasonic disperser, a high-pressure homogenizer, can be used as needed.

  Preferred examples of the organic solvent include alcohol solvents, ketone solvents, and ether solvents. Regarding the details of these organic solvents, the description in paragraph [0109] of JP2011-42150A can be applied. Among these, a ketone solvent such as methyl ethyl ketone and an alcohol solvent such as isopropyl alcohol are preferable, and isopropyl alcohol and methyl ethyl ketone are preferably used from the viewpoint of mildly changing the polarity at the phase inversion from oil to water. By using the solvent in combination, it is possible to obtain self-dispersing polymer particles having a fine particle size with high dispersion stability without aggregation and sedimentation and fusion between particles.

The neutralizing agent is used so that a part or all of the dissociable group is neutralized and the self-dispersing polymer forms a stable emulsified or dispersed state in water. When the self-dispersing polymer has an anionic dissociative group (for example, carboxyl group) as a dissociable group, examples of the neutralizing agent used include basic compounds such as organic amine compounds, ammonia, and alkali metal hydroxides. It is done. Regarding the details of these neutralizing agents, the description in paragraph number [0110] of JP-A-2011-42150 can be applied. Among these, sodium hydroxide, potassium hydroxide, triethylamine, and triethanolamine are preferable from the viewpoint of stabilizing the dispersion of the self-dispersing polymer particles in water.
These basic compounds are preferably used in an amount of 5 to 120 mol% with respect to 100 mol% of the dissociable group. Details of the ratio here are described in paragraph number [0111] of Japanese Patent Application Laid-Open No. 2011-42150.

  In step (2), an aqueous dispersion of polymer particles is obtained by distilling off the organic solvent from the dispersion obtained in step (1) by a conventional method such as distillation under reduced pressure and phase-inversion into an aqueous system. Can do. The organic solvent in the obtained aqueous dispersion has been substantially removed, and the amount of the organic solvent is preferably 0.2% by mass or less, more preferably 0.1% by mass or less.

The average particle size of the polymer particles (particularly self-dispersing polymer particles) is preferably in the range of 10 nm to 400 nm in terms of volume average particle size, more preferably in the range of 10 nm to 200 nm, still more preferably in the range of 10 nm to 100 nm, particularly preferably. It is in the range of 10 nm to 50 nm. Manufacturability is improved when the average particle size is 10 nm or more. Moreover, storage stability improves because an average particle diameter is 400 nm or less. Moreover, there is no restriction | limiting in particular regarding the particle size distribution of a polymer particle, Any of what has a wide particle size distribution or a monodispersed particle size distribution may be sufficient. Two or more water-insoluble particles may be mixed.
The average particle size and particle size distribution of the polymer particles are determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso Co., Ltd.). It is what

The glass transition temperature (Tg) of the polymer particles is preferably from −60 ° C. to 70 ° C., more preferably from 0 ° C. to 60 ° C., and even more preferably from 20 ° C. to 40 ° C. from the viewpoint of storage stability of the inkjet ink composition.
When the glass transition temperature is within the range, it is difficult for the image to be hard or sticky, the texture such as touch feeling (for example, the image is not hard or sticky), and the image is scratch resistant. Can be further improved.

The polymer particles (particularly self-dispersing polymer particles) can be used alone or in combination of two or more. Two or more types of polymer particles may be included, and particles composed of a polymer in which two or more types are mixed or bonded may be used.
The content of the polymer particles in the inkjet ink composition is preferably 1 to 30% by mass and more preferably 5 to 15% by mass with respect to the total amount of the ink from the viewpoint of image scratch resistance.

(Photocurable polymer)
The inkjet ink composition in the present invention contains at least one water-soluble photocurable polymer. The water-soluble photocurable polymer is a polymer that exhibits solubility in water and is cured by causing a crosslinking reaction upon irradiation with light. Here, water-soluble means to dissolve 1% by mass or more in 20 ° C. water.

  Examples of the photocurable polymer include a homopolymer or a copolymer having a repeating unit including a partial structure represented by the following general formula (1) (hereinafter, also referred to as “specific copolymer (a)”). And a polymer having an ethylenically unsaturated double bond.

[1] Specific copolymer (a)

In General Formula (1), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R ^a and R ^b is an alkyl group having 1 to 4 carbon atoms. Represents. R ^a and R ^b may combine with each other to form a 4- to 6-membered alicyclic structure. * Indicates a binding site to the main chain or side chain in the polymer compound.

The alkyl group having 1 to 4 carbon atoms represented by R ^a or R ^b may have a linear structure or a branched structure. Specifically, a methyl group, an ethyl group, a propyl group, isopropyl Group, butyl group, isobutyl group, sec-butyl group, or t-butyl group. Among these, R ^a or R ^b is preferably an alkyl group having 1 to 2 carbon atoms, that is, a methyl group or an ethyl group, and particularly preferably an alkyl group having 1 carbon atom (methyl group).

The alkyl group represented by R ^a or R ^b may be unsubstituted or substituted, but is preferably unsubstituted.

R ^a and R ^b may be bonded to each other to form a 4- to 6-membered alicyclic structure.

As R ^a and R ^b , an embodiment in which both are alkyl groups having 1 to 4 carbon atoms, or an embodiment in which R ^a and R ^b are bonded to each other to form a 4- to 6-membered alicyclic structure. It is more preferable that both R ^a and R ^b are alkyl groups having 1 to 2 carbon atoms, and it is still more preferable that both R ^a and R ^b are alkyl groups having 1 carbon atom.

  Specific examples of the partial structure represented by the general formula (1) are shown below. However, the present invention is not limited to these.

  The specific copolymer (a) may have an aspect having a plurality of partial structures represented by the general formula (1) in the side chain.

  The structure having a partial structure represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2).

In General Formula (2), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R ^a and R ^b is an alkyl group having 1 to 4 carbon atoms. Represents. R ^a and R ^b may combine with each other to form a 4- to 6-membered alicyclic structure. R ^c represents a hydrogen atom or a methyl group. Z represents a single bond, —COO — ** or —CONR ^d — **, R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and “**” represents a bonding position with X. Represents. X represents an alkylene group or an aralkylene group.

In General Formula (2), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R ^a and R ^b represents an alkyl group having 1 to 4 carbon atoms. Represent. R ^a and R ^b may combine with each other to form a 4- to 6-membered ring structure.
^{R a} and ^{R b} in the general formula (2) is respectively the same meanings as ^{R a} and ^{R b} in the general formula (1), and preferred ranges are also the same.

In the general formula (2), R ^c represents a hydrogen atom or a methyl group. R ^c is preferably a methyl group.
In General Formula (2), Z represents a single bond, —COO — **, or —CONR ^d — **, R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and “** "Represents a bonding position with X. Z is preferably -COO-**.

R ^d in —CONR ^d — ** represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms represented by R ^d may have a linear structure or a branched structure, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. , Isobutyl group, sec-butyl group, or t-butyl group. R ^d is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, that is, a methyl group or an ethyl group, and particularly preferably a hydrogen atom. If R ^d represents an alkyl group, even if the alkyl group optionally having a substituent, may not have a substituent, but preferably does not have a substituent.

  In General formula (2), X represents an alkylene group or an aralkylene group as a divalent organic group. Especially, as X, a C2-C20 alkylene group or a C6-C12 aralkylene group is preferable. X is more preferably an alkylene group, and particularly preferably an alkylene group having 2 to 20 carbon atoms.

  When X represents an alkylene group, the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. When the carbon number of the alkylene group represented by X is within this range, the mobility of the partial structure represented by the general formula (1) existing at the end of the side chain of the specific copolymer (a) is improved, and the image Water resistance and solvent resistance, and adhesion of an image to a recording medium are further improved.

  The alkylene group represented by X may have a linear structure, a branched chain in the alkylene chain, or a cyclic structure. The alkylene group represented by X may contain a bond selected from —O—, —COO—, —OC (═O) —, and —CONH— in the alkylene chain. Furthermore, the alkylene group represented by X may be substituted with an alkyl group having 4 or less carbon atoms, a hydroxyl group, or a chlorine atom.

In the repeating unit represented by the general formula (2), R ^a and R ^b are each independently an alkyl group having 1 to 2 carbon atoms, R ^c is a methyl group, and Z is —COO — **. It is preferable that X is an alkylene group having 2 to 12 carbon atoms.

The ratio of the repeating unit including the partial structure represented by the general formula (1) in the specific copolymer (a) (preferably the repeating unit represented by the general formula (2)) is formed by the ink composition. The cured film (image) is appropriately selected according to the intended properties. That is,
The ratio of the repeating unit containing the partial structure represented by the general formula (1) (preferably the repeating unit represented by the general formula (2)) is from the viewpoint of the strength (durability) and flexibility of the recorded image. 20 mass%-70 mass% is preferable with respect to the total mass of a specific copolymer (a), 30 mass%-70 mass% is more preferable, and 40 mass%-60 mass% is still more preferable.
When the content of the repeating unit including the partial structure represented by the general formula (1) contained in the specific copolymer (a) is within the above range, the image strength is improved. In addition, when forming the image excellent in the softness | flexibility, the one where the ratio of the repeating unit containing the partial structure represented by General formula (1) is low is preferable.
The specific copolymer (a) may contain only one type of repeating unit having a partial structure represented by the general formula (1), or may contain two or more types.

The repeating unit including the partial structure represented by the general formula (1) is obtained by homopolymerizing the monomer including the partial structure represented by the general formula (1) or copolymerizing it as one of the copolymerization components. Thus, it can be introduced into the specific copolymer (a). When the repeating unit including the partial structure represented by the general formula (1) is a repeating unit represented by the general formula (2), the following general formula (2 ′) is used for the synthesis of the specific copolymer (a). ) Can be used.
Moreover, the repeating unit containing the partial structure represented by General formula (1) can also be introduce | transduced by the method using a polymer reaction. Examples of such a method include a method obtained by reacting a prepolymer having a primary amino group with a corresponding anhydride, a functional group which reacts with a functional group in the prepolymer to form a bond, Examples thereof include a method of reacting a compound having a partial structure represented by the formula (1) with a prepolymer.

In the general formula ^{(2 '), R a,} R b, R c, Z, and X are each the same meaning as ^{R a, R b, R c} , Z, and X in the general formula (2), a preferred range Is the same.

  Preferable examples of the monomer represented by the general formula (2 ′) include monomers (2′-1) to (2′-12) shown below. It is not limited.

  Monomers containing a partial structure represented by the general formula (1) represented by the monomers (2′-1) to (2′-12) include, for example, JP-A-52-988, It can be produced with reference to the method described in JP-A-4-251258.

As the specific copolymer (a) in the present invention, R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^c represents a methyl group, and Z represents —COO—. A homopolymer or copolymer having a repeating unit containing a partial structure represented by the general formula (1) when ** is represented and X represents an alkylene group having 2 to 12 carbon atoms is preferred.

(Repeating unit having a hydrophilic group)
The specific copolymer (a) preferably includes a repeating unit having a hydrophilic group.
The hydrophilic group is not particularly limited as long as it is a group having a function of enhancing the hydrophilicity of the specific copolymer (a), and may be a nonionic hydrophilic group or an ionic hydrophilic group (for example, , An anionic hydrophilic group or a cationic hydrophilic group).

  The nonionic hydrophilic group is not particularly limited. For example, a residue obtained by removing one hydrogen atom from a heterocyclic structure containing a nitrogen atom or an oxygen atom, an amide group, a carbamoyl group, an alkyl-substituted carbamoyl group, an alcoholic hydroxyl group, Or nonionic hydrophilic groups, such as group which has a polyalkyleneoxy structure, are mentioned.

  Examples of the heterocyclic structure in the residue obtained by removing one hydrogen atom from a heterocyclic structure containing a nitrogen atom or an oxygen atom include lactones such as γ-butyrolactone; cyclic ureas such as 2-pyrrolidone and ethylene urea; ethylene carbonate, And cyclic carbonates such as propylene carbonate, and cyclic ethers such as tetrahydrofuran and 1,4-dioxane;

  As the amide group, an amide group having 2 to 10 carbon atoms is preferable, and a hydrogen atom is preferably bonded to a nitrogen atom in the amide group.

  The alkyl-substituted carbamoyl group is a monoalkylcarbamoyl group in which a hydrogen atom bonded to a nitrogen atom of a carbamoyl group is substituted with an alkyl group, or two hydrogen atoms bonded to a nitrogen atom of a carbamoyl group are substituted with an alkyl group And a dialkylcarbamoyl group formed. This alkyl group may further have a substituent such as a hydroxyl group. Among these alkyl-substituted carbamoyl groups, a C1-C8 alkyl group or a monoalkylcarbamoyl group substituted with a C1-C4 alkyl group substituted with a hydroxyl group is preferable.

  Although it does not specifically limit as group which has a polyalkyleneoxy structure, The polyalkyleneoxy structure which has a C1-C4 alkyleneoxy group in a repeating unit is preferable. One type of alkyleneoxy group in the polyalkyleneoxy structure may be used, or a plurality of types of alkyleneoxy groups may be combined. The terminal group of the polyalkyleneoxy structure is preferably a hydroxyl group or an alkoxy group, more preferably a hydroxyl group or a methoxy group.

  Although it does not specifically limit as an ionic hydrophilic group, For example, ionic hydrophilic groups, such as a carboxyl group, a sulfo group, a phosphoric acid group, a phosphonic acid group, a phenolic hydroxyl group, or a quaternary ammonium group, are mentioned. This ionic hydrophilic group may form a salt.

  When the ionic hydrophilic group forms a salt, examples of the counter salt include onium salts such as alkali metal salts (Li, Na, K, etc.), ammonium salts, pyridinium salts, and phosphonium salts. Among these, alkali metal salts (Li, Na, K, etc.) or ammonium salts are preferable.

  Among these hydrophilic groups, an amide group, a carbamoyl group, an alkyl-substituted carbamoyl group, an alcoholic hydroxyl group, a group having a polyalkyleneoxy structure, a carboxyl group, a sulfo group, and a salt thereof are preferable. A carbamoyl group, a carboxyl group, a sulfo group, and salts thereof are more preferable. Particularly preferred are carboxyl groups and salts thereof.

  The repeating unit having a hydrophilic group is preferably a repeating unit represented by the following general formula (3).

In general formula (3), R ^cy represents a hydrogen atom or a methyl group. Z ^y represents —COO — ***, —CONR ^dy — ***, or a single bond, and R ^dy represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^y represents a group selected from the group consisting of a single bond, an alkylene group, an arylene group, and an aralkylene group. A represents a hydrophilic group. “***” represents the position where Z ^y is bonded to R ^y .

The general formula (3) will be described in detail.
In general formula (3), R ^cy represents a hydrogen atom or a methyl group.
In the general formula (3), Z ^y represents —COO — ***, —CONR ^dy — ***, or a single bond, and is preferably —COO — ***.

R ^dy represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may have a linear structure or a branched structure. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group. R ^dy is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, that is, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.

R ^dy may be unsubstituted or may have a substituent, but is preferably unsubstituted. Examples of the substituent that R ^dy may have include an aryl group having 6 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom (F, Cl, Br, I, etc.), and the like. Is mentioned.

In General Formula (3), R ^y represents a single bond or a group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, an alkylene group having 1 to 20 carbon atoms, and a group having 6 to 20 carbon atoms. An arylene group or an aralkylene group having 7 to 20 carbon atoms is preferable.
When ^Ry is a group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, these groups may or may not have a substituent. The alkylene group, arylene group, and aralkylene group represented by R ^y may have an ether bond, an ester bond, an amide bond, or a urethane bond in the structure.
In the general formula (3), R ^y is preferably a single bond.

When ^Ry is a group selected from the group consisting of an alkylene group, an arylene group, and an aralkylene group, these groups may further have a substituent. Examples of the substituent include an aryl group having 6 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom (F, Cl, Br, I, etc.) and the like.

When ^Ry is an alkylene group having 1 to 20 carbon atoms, the alkylene group may have a linear structure, a branched structure, or a cyclic structure. When ^Ry is an alkylene group, the carbon number is more preferably 2 to 12, and still more preferably 2 to 8. Specific examples of the alkylene group for R ^y include —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —CH ₂ —, —CH ₂ C (CH ₃ ) ₂ CH ₂ —, —C. _{6 H 12 -, - C 4} H 7 (C 4 H 9) C 4 H 8 -, C 18 H 36 -, 1,4-trans- cyclohexylene _{group, -C 2 H 4 -OCO-C} 2 H 4 _{-, - C 2 H 4 -OCO} -, - C 2 H 4 -O-C 5 H 10 -, - CH 2 -O-C 5 H 9 (C 5 H 11) -, - C 2 H 4 -CONH _{-C 2 H 4 -, - C} 4 H 8 -OCONH-C 6 H 12 -, - CH 2 -OCONHC 10 H 20 -, - CH 2 CH (OH) CH 2 - and the like.

When ^Ry is an arylene group having 6 to 20 carbon atoms, the arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms. preferable. Specific examples of the arylene group represented by R ^y include a phenylene group, a biphenylene group, —C ₆ H ₄ —CO—C ₆ H ₄ —, a naphthylene group, and the like.

When ^Ry is an aralkylene group having 7 to 20 carbon atoms, the aralkylene group preferably has 7 to 18 carbon atoms, more preferably 7 to 14 carbon atoms, and particularly preferably 7 to 10 carbon atoms. preferable. Specific examples of the aralkylene group represented by R ^y _{is, -C 3 H 6 -C 6 H} 4 -, - C 2 H 4 -C 6 H 4 -C 6 H 4 -, - CH 2 -C 6 H _{4 -C 6 H 4 -C 2 H} 4 -, - C 2 H 4 -OCO-C 6 H 4 - , and the like.

  In the general formula (3), examples of the hydrophilic group represented by A include the hydrophilic groups described above, and preferred ranges thereof are also the same.

When the specific copolymer (a) has a repeating unit represented by the general formula (3), the ratio of the repeating unit represented by the general formula (3) in the specific copolymer (a) is as follows. is there.
When the hydrophilic group represented by A in the general formula (3) is an ionic hydrophilic group, the ratio of the repeating unit represented by the general formula (3) is based on the entire specific copolymer (a). 5% by mass to 50% by mass is preferable, 5% by mass to 40% by mass is more preferable, and 1% by mass to 20% by mass is particularly preferable.
In the case where the hydrophilic group represented by A in the general formula (3) is a nonionic hydrophilic group, the ratio of the repeating unit represented by the general formula (3) is based on the entire specific copolymer (a). 20% by mass to 95% by mass is preferable, 30% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is particularly preferable.

  The repeating unit represented by the general formula (3) is derived from a monomer represented by the following general formula (3 ′). By including this monomer as a copolymerization component, the repeating unit (3) is introduced into the specific copolymer (a).

In the general formula ^{(3 '), R cy,} Z y, R y, and A, ^R cy in the general formula ^(3), Z y, are each and ^{R y,} and A synonymous, and preferred ranges are also the same .

Preferable examples of the monomer represented by the general formula (3 ′) include the following compounds. However, the present invention is not limited to these.
Methoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, poly (ethylene glycol-co-propylene glycol) (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol (meth) Acrylate (meth) acryloyloxyethyl ethylene urea, vinylpyrrolidone, 3- (meth) acryloyloxy-γ-butyrolactone, acrylamide, tert-butylacrylamide, N, N-dimethyl (meth) acrylamide, diacetone acrylamide, (meth) Sodium acrylate, potassium (meth) acrylate, tetrabutylammonium (meth) acrylate, mono (meth) acryloyloxyethyl succinic acid, Sodium (meth) acryloyloxyethyl succinate, sodium mono (meth) acryloyloxyethyl phthalate, (meth) acryloyloxyethyl acid phosphate, sodium 2-acrylamido-2-methylpropanesulfonate, 2-acrylamide- Examples include 2-methylpropane sulfonic acid, styrene sulfonic acid, sodium styrene sulfonate, and vinyl benzoic acid.

  As the monomer represented by the general formula (3 ′), a commercially available compound can be used, and it can be produced by a generally known and commonly used method.

  In the present invention, in addition to the monomer represented by the general formula (3 ′), unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, and fumaric acid, and anhydrides thereof, and further derived therefrom. Dicarboxylic acid salts can also be preferably used.

The ratio of the repeating unit having a hydrophilic group in the specific copolymer (a) varies depending on the type of the hydrophilic group, but the specific copolymer (a) may be water-soluble. preferable. Here, the specific copolymer (a) being “water-soluble” means that the specific copolymer (a) can be dissolved in 3% by mass or more in water at 25 ° C.
The ratio of the repeating unit having a hydrophilic group in the specific copolymer (a) is preferably 8% by mass to 25% by mass, and 10% by mass to 23% by mass with respect to the entire specific copolymer (a). More preferably, 10% by mass to 20% by mass is even more preferable.
When the content of the repeating unit having a hydrophilic group is within the above range, the polarity of the specific copolymer (a) is appropriately maintained, and suitable water resistance is obtained.
The specific copolymer (a) may contain only one type of repeating unit having a hydrophilic group, or may contain two or more types.

(Repeating unit having a hydrophobic group)
The specific copolymer (a) preferably includes a repeating unit having a hydrophobic group. By including the repeating unit having a hydrophobic functional group, the polarity of the specific copolymer (a) is appropriately maintained, and the ink image formed by the ink composition is excellent in water resistance and non-absorbing. The adhesiveness to the recording medium is excellent.
The repeating unit having a hydrophobic group is derived from a vinyl monomer having a weight average molecular weight of 10,000 or more and a solubility in water at 25 ° C. of less than 1.0% by mass when it is a homopolymer of only this repeating unit. These repeating units are preferred. Among these, a repeating unit derived from a monomer selected from alkyl esters and (aralkyl esters) of (meth) acrylic acid is preferably used.
Moreover, from the viewpoint of adjusting the polarity of the specific copolymer (a) to an appropriate range, the hydrophobic group is preferably an alkyl group having 5 to 22 carbon atoms, and an alkyl group having 8 to 22 carbon atoms. More preferred is an alkyl group having 8 to 14 carbon atoms. That is, in the case of alkyl acrylate, it is an ester having an alkyl group having 4 to 19 carbon atoms, and an ester having an alkyl group having 4 to 13 carbon atoms is preferred. In the case of alkyl methacrylate, it is an ester having an alkyl group having 4 to 18 carbon atoms, and an ester having an alkyl group having 4 to 10 carbon atoms is preferred.
The alkyl group may be linear or branched, and may be cyclic. Further, aralkyl esters such as benzyl group and phenoxyethyl group may be used.

The repeating unit having a hydrophobic group is exemplified below. However, the present invention is not limited to these.
Examples of the repeating unit having a hydrophobic group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, (Meth) acrylic acid such as cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acetoacetoxyethyl (meth) acrylate Repeating units derived from alkyl ester, styrene and α- methyl styrene, 4 repeating units derived from a styrene compound methyl styrene, repeating units derived from a vinyl ether-based compounds such as chloroethyl vinyl ether.
Among these, the repeating unit having a hydrophobic group is a (meth) acrylic acid ester (for example, n-propyl methacrylate, isopropyl methacrylate, n-butyl (meth)) substituted with an alkyl group having 5 to 22 carbon atoms in total. Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, Repeating units derived from stearyl (meth) acrylate, cyclohexyl methacrylate, etc. are preferred, n-propyl methacrylate, isopropyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t More preferred are repeating units derived from rt-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, benzyl methacrylate, phenoxyethyl (meth) acrylate, and the like. -Repeating units derived from butyl methacrylate, isobutyl methacrylate, tert-butyl (meth) acrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate and phenoxyethyl (meth) acrylate are particularly preferred.

The specific copolymer (a) may contain only one type of repeating unit having a hydrophobic group, or may contain two or more types.
The ratio of the repeating unit having a hydrophobic group in the specific copolymer (a) is preferably 5% by mass to 72% by mass, more preferably 20% by mass to 65% by mass from the viewpoint of reducing the polarity of the copolymer. Preferably, 25% by mass to 60% by mass, and most preferably.

Specific copolymer (a) preferably has a SP value of ^{20.7MPa 1/2 ~23.0MPa 1/2,} preferably from 21.2MPa ^1/2 ~22.8MPa 1/2, 21.5MPa ^{1/2 to} 22.5 MPa ^1/2 is particularly preferable.
The SP value is a solubility parameter calculated by the Okitsu method (adhesion 38: 6 page 6 (1994) polymer publication society), and the molar attractive constant and molar volume are determined for each unit in the molecular structure. The estimated value proposed by Okitsu is given. In addition, when calculating the SP value of the polymer, the carboxylic acid in (meth) acrylic acid is calculated in an unneutralized state, and the SP value in this specification is the value calculated by this method. Used.

Hereinafter, SP values of typical monomer units used in the specific copolymer (a) are described. The numerical value described in parentheses after the monomer name is the SP value, and the unit is MPa ^1/2 .
The following monomer 1 (24.41), the following monomer 2 (23.22), the following monomer 3 (22.75), methacrylic acid (24.02), 2-hydroxyethyl methacrylate (22.89), 2-hydroxyethyl Acrylamide (32.87) methyl methacrylate (19.5), n-butyl methacrylate (18.33), isobutyl methacrylate (17.76), tert-butyl methacrylate (17.97), 2-ethylhexyl methacrylate (17.30) ), Stearyl methacrylate (17.08), 2-hydroxyethyl methacrylate (22.89), tetrahydrofurfuryl methacrylate (21.29), cyclohexyl methacrylate (18.79), benzyl methacrylate (20.21), 2-phenoxy Echi Methacrylate (20.23), isobornyl methacrylate (18.09)

The weight average molecular weight of the specific copolymer (a) contained in the ink composition of the present invention is preferably in the range of 5,000 to 150,000 from the viewpoint of water resistance, and from the viewpoint of improving water resistance and dischargeability. A range of 5,000 to 100,000 is more preferable.
The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (4.6 mm ID × 15 cm, Tosoh Corporation) as columns and THF (tetrahydrofuran) as an eluent. And the column oven was set at a set temperature of 40 ° C. Standard polystyrene was used for calculation of molecular weight.

As the photocurable polymer in the present invention, R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^c represents a methyl group, and Z represents —COO — **. And a repeating unit derived from at least one monomer selected from the following group a and a repeating unit containing a partial structure represented by the general formula (1) when X represents an alkylene group having 2 to 12 carbon atoms: Are more preferable.
[Group a: (meth) acrylic acid and / or salt thereof, N-isopropylacrylamide, polyethylene glycol of (meth) acrylic acid, polyethylene glycol monoalkyl ether, ester compound of methanol, vinyl alcohol, N-vinylpyrrolidone, hydroxyethyl (Meth) acrylate, carboxyethyl (meth) acrylate, etc.)

  Hereinafter, specific examples [Exemplary compounds (A-1) to (A-24), (P-1) to (P-10)] of the specific copolymer (a) in the present invention are shown. However, the present invention is not limited to this. In addition, SP value shows SP value of a copolymer and is a value obtained by the measuring method or calculation method as stated above, respectively.

The details of the abbreviations described in Table 1 are as follows.
MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries)
MAA-Na: Methacrylic acid sodium salt (generated by neutralizing a polymer copolymerized with methacrylic acid)
BMA: n-butyl methacrylate (manufactured by Wako Pure Chemical Industries)
・ HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries)
-HEAA: hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
IBMA: Isobutyl methacrylate (Wako Pure Chemical Industries, Ltd.)
・ TBMA: tert-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
・ IBOMA: Isoboronyl methacrylate (Wako Pure Chemical Industries, Ltd.)
C18MA: Octadecyl methacrylate (manufactured by Wako Pure Chemical Industries)
CyHMA: cyclohexyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
PEMA: Phenoxyethyl methacrylate (NK ester PHE-1G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
EHMA: 2-ethylhexyl methacrylate (Wako Pure Chemical Industries, Ltd.)
・ BnMA: benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

  The specific copolymer (a) is, for example, a monomer for forming a repeating unit having a partial structure represented by the general formula (1) and a single amount for forming a repeating unit having a hydrophilic group And a monomer for forming a repeating unit having a hydrophobic group are obtained by polymerizing by a known polymerization method, and neutralized with an alkali metal hydroxide or the like as necessary. be able to. Specifically, for example, a method according to the polymerization method described in JP-A-52-988, JP-A-55-154970, Langmuir Vol. 18, No. 14, pages 5414-5421 (2002), etc. A copolymer (a) can be produced.

[2] Polymer having an ethylenically unsaturated double bond As another example of the photocurable polymer, a polymer having an ethylenically unsaturated double bond will be described. The polymer having an ethylenically unsaturated double bond is a polymer having at least one ethylenically unsaturated double bond in one molecule, for example, a polyoxyalkyl-terminated mono- or di (meth) acrylate compound, or poly A terminal mono- or vinyl compound of oxyalkyl, a trifunctional (meth) acrylate of trimethylolpropane, a trifunctional (meth) acrylate of glycerol, acrylic-modified polyvinyl alcohol, or the like can be used.

  As the polymer having an ethylenically unsaturated double bond, a commercially available product may be used. Examples of commercially available products include poly (1,4-butanediol) divinyl ether manufactured by Aldrich, manufactured by Aldrich. Allyl alcohol 1,2-butoxylate-block-ethoxylate, Aldrich trimethoxylol propane ethoxylate triacrylate, Aldrich polyethylene glycol divinyl ether, Aldrich polyethylene glycol methacrylate, Aldrich Examples thereof include polyethylene glycol dimethacrylate, glycerol propoxylate manufactured by Aldrich, and O-106 manufactured by Chukyo Yushi Co., Ltd.

In the inkjet ink composition of the present invention, the ratio (P / CP) of the content (P) of the polymer particles to the content (CP) of the above-described photocurable polymer is 9.5 / 0. The range of 5 to 2/8 is preferable, and the range of 9/1 to 5/5 is more preferable.
When the above ratio (P / CP) is within the above range, the formed image has good softness that does not greatly impair the flexibility of the recording substrate while having good resistance to scratching. It also has both sex and draping properties.

(Polyhydric alcohol compound, amide compound, or amine compound)
The inkjet ink composition in the present invention preferably contains at least one compound selected from the group consisting of a polyhydric alcohol compound, an amide compound, and an amine compound. These compounds function as a humectant for the ink composition.

Polyhydric alcohol compounds, amide compounds, and amine compounds are all more preferably compound vapor pressure (P _w) is less than 1Pa at 25 ° C.. By having a vapor pressure of less than 1 Pa, it is difficult to evaporate and remains in the formed image, so that the drapability of the image can be further improved.

  In addition, the polyhydric alcohol compound, the amide compound, and the amine compound all preferably have a melting point of less than 25 ° C. A melting point (mp) of less than 25 ° C. indicates a liquid state at room temperature.

Specific examples of the polyhydric alcohol compound, the amide compound, and the amine compound include the following compounds. Incidentally, _{P w} in parentheses indicate a vapor pressure at 25 ° C..

The polyhydric alcohols include glycerol _{(P w: 0.01Pa, mp:} 17.8 ℃), diglycerol _(P w: 0.01 Pa or less, liquid at 25 ° C.), polyglycerol _(P w: 0. 01 Pa or less and liquid at 25 ° C.), alkyleneoxy alcohol, alkyleneoxyalkyl ether, and the like.

Examples of the alkyleneoxy alcohol include compounds represented by the following structural formula (1).

In the structural formula (1), l, m, and n each independently represent an integer of 1 or more and satisfy l + m + n = 3-15. Among them, when l + m + n is 3 or more, there is little adverse effect on image abrasion resistance, and when it is 15 or less, the discharge property can be kept good. Especially, 3-12 are preferable and 3-10 are more preferable. AO represents ethyleneoxy (sometimes abbreviated as EO) and / or propyleneoxy (sometimes abbreviated as PO), and among them, a propyleneoxy group is preferable. Each AO of (AO) ₁ , (AO) _m , and (AO) _{n in} the structural formula may be the same or different.
Details of the compound represented by the structural formula (1) are described in paragraph numbers [0121] to [0125] of JP2011-42150A. Examples of the compound represented by the structural formula (1) include the following compounds. The numerical value in parentheses indicates the SP value.

  As the alkylene oxide adduct of glycerin, a commercially available product may be used. For example, as polyoxypropylated glycerin (ether of polypropylene glycol and glycerin), Sanniks GP-250 (average molecular weight 250), Examples include GP-400 (average molecular weight 400), GP-600 (average molecular weight 600) [manufactured by Sanyo Chemical Industries, Ltd.], and paragraph [0126] of the publication.

Examples of the amide compound include urea (P _w : 80 Pa, mp: 132 ° C.).

Examples of the amine compound include polyethyleneimine (P _w : less than 1 Pa, liquid at 25 ° C.).

  Among these, glycerin, diglycerin, and polyethyleneimine are preferable from the viewpoint of further improving the flexibility of the cured image and thus the drapeability.

The total content of the polyhydric alcohol compound, the amide compound, and the amine compound in the inkjet ink composition of the present invention is in the range of 1% by mass to 15% by mass with respect to the total mass of the inkjet ink composition. The range of 1% by mass to 10% by mass is more preferable, and the range of 2% by mass to 10% by mass is more preferable.
That the total content of the polyhydric alcohol compound, the amide compound, and the amine compound is 1% by mass or more indicates that these compounds are substantially contained. Moreover, it is advantageous from a viewpoint of abrasion resistance because total content is 15 mass% or less.

In the inkjet ink composition of the present invention, the ratio (p: q) between the content p of the photocurable polymer described above and the total content q of the polyhydric alcohol compound, the amide compound, and the amine compound is as follows. The mass ratio is preferably in the range of 20: 1 to 1: 8, and more preferably in the range of 8: 1 to 1: 5.
When the ratio (p: q) is within the above range, the formed image has good flexibility that does not greatly impair the flexibility of the recording substrate while having good resistance to scratching. As a result, it also has a drape property.

(Coloring agent)
The inkjet ink composition in the present invention can contain at least one colorant. As the colorant, pigments, dyes and the like are suitable, and among these, pigments are preferred from the viewpoint of light resistance of images. There is no restriction | limiting in particular as a pigment, According to the objective, it can select suitably, For example, any of an organic pigment and an inorganic pigment may be sufficient. The pigment is preferably a pigment that is almost insoluble or hardly soluble in water from the viewpoint of ink colorability.

Examples of organic pigments include polycyclic cyclic compounds such as azo lakes, azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments. Pigments: Dye lakes such as basic dye type lakes and acid dye type lakes; nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments and the like. Examples of the inorganic pigment include titanium oxide, iron oxide, and carbon black. Any pigment that is not described in the color index can be used as long as it is dispersible in the aqueous phase.
In addition, pigments that have been surface-treated with a surfactant, a polymer dispersant, or the like, or graft carbon can also be used.
Among these, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, and carbon black pigments are particularly preferable.

The ink-jet ink composition in the present invention may contain a water-dispersible pigment as a colorant.
Specific examples of the water-dispersible pigment include the following pigments (1) to (4).
(1) An encapsulated pigment, that is, a polymer dispersion in which a pigment is contained in polymer particles. More specifically, the pigment is coated with a hydrophilic water-insoluble resin and is made hydrophilic by a resin layer on the pigment surface. (2) Self-dispersed pigment, that is, having at least one hydrophilic group on the surface and having at least one of water dispersibility and water solubility in the absence of a dispersant. (3) Resin-dispersed pigment, that is, a water-soluble water having a weight average molecular weight of 50,000 or less. (4) Surfactant-dispersed pigment, that is, a pigment dispersed by a surfactant

Here, (1) the encapsulated pigment will be described in detail.
The encapsulated pigment resin is not limited, but is a polymer compound that has self-dispersibility or solubility in a mixed solvent of water and a water-soluble organic solvent and has an anionic group (acidic). Is preferred. This resin usually has a number average molecular weight of preferably about 1,000 to 100,000, particularly preferably about 3,000 to 50,000. Further, this resin is preferably one that dissolves in an organic solvent to form a solution. If the number average molecular weight of the resin is within the above range, it can exhibit a function as a coating film for the pigment or as a coating film when used as an ink. The resin is preferably used in the form of an alkali metal or organic amine salt.

Specific examples of encapsulated pigment resins include thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated polyester, phenol, silicone, or fluorine. Resins: Polyvinyl resins such as vinyl chloride, vinyl acetate, polyvinyl alcohol, or polyvinyl butyral, polyester resins such as alkyd resins and phthalic resins, melamine resins, melamine formaldehyde resins, aminoalkyd co-condensation resins, urea resins, urea Examples thereof include amino materials such as resins, and materials having an anionic group such as copolymers or mixtures thereof.
Among these resins, an anionic acrylic resin is, for example, an acrylic monomer having an anionic group (hereinafter referred to as “anionic group-containing acrylic monomer”) and, if necessary, the anionic group-containing acrylic monomer. It is obtained by polymerizing another polymerizable monomer in a solvent. Examples of the anionic group-containing acrylic monomer include an acrylic monomer having one or more anionic groups selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic group. Among these, an acrylic monomer having a carboxyl group is used. Particularly preferred. Specific examples of the acrylic monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid and the like. Among these, acrylic acid or methacrylic acid is preferable.

  The encapsulated pigment can be produced by the conventional physical and chemical methods using the above components. For example, as described in JP-A-9-151342, JP-A-10-140065, JP-A-11-209672, JP-A-11-172180, JP-A-10-25440, or JP-A-11-43636. It can be manufactured by a method. Specific examples include the phase inversion emulsification method and the acid precipitation method described in JP-A-9-151342 and JP-A-10-140065. Among them, the phase inversion emulsification method is preferable in terms of dispersion stability. preferable. The phase inversion emulsification method will be described later.

Self-dispersing pigments are also a preferred example. The self-dispersing pigment refers to a large number of hydrophilic functional groups and / or salts thereof (hereinafter referred to as “dispersibility-imparting groups”) directly on the pigment surface or indirectly via an alkyl group, an alkyl ether group, an aryl group, or the like. Are pigments that can be dispersed in an aqueous medium without using a dispersant for dispersing the pigment. Here, “dispersed in an aqueous medium without using a dispersant” means that the pigment can be dispersed in an aqueous medium without using a dispersant for dispersing the pigment.
Inks containing self-dispersing pigments as colorants usually do not need to contain dispersants to disperse the pigments, so there is almost no foaming due to defoaming loss due to the dispersants, and ejection stability It is easy to prepare an ink that excels. The dispersibility-imparting groups to be bonded to the surface of the self-dispersing _{pigment, -COOH, -CO, -OH, -SO} 3 H, can be exemplified _-PO 3 _{H 2,} and a quaternary ammonium and salts thereof The dispersibility-imparting group is bonded by subjecting the pigment to physical treatment or chemical treatment to bond (graft) the active species having the dispersibility-imparting group or the dispersibility-imparting group to the pigment surface. Examples of physical treatment include vacuum plasma treatment. In addition, as the chemical treatment, for example, a wet oxidation method in which the pigment surface is oxidized with an oxidizing agent in water, a method in which a carboxyl group is bonded via a phenyl group by bonding p-aminobenzoic acid to the pigment surface, Etc. can be exemplified.

In the present invention, for example, a self-dispersing pigment that is surface-treated by oxidation treatment with hypohalous acid and / or hypohalite or oxidation treatment with ozone can be mentioned as a preferred example. Commercially available products may be used as the self-dispersing pigment. Specifically, Microjet CW-1 (trade name; manufactured by Orient Chemical Industry Co., Ltd.), CAB-O-JET200, CAB-O-JET300 (trade name) ; Manufactured by Cabot Corporation).
As the pigment, a water-insoluble resin among the pigment dispersant is used, and an encapsulated pigment in which at least a part of the surface of the pigment is coated with the water-insoluble resin, for example, a polymer emulsion in which the pigment is contained in water-insoluble resin particles is preferable. More specifically, a water-dispersible pigment that can be dispersed in water by covering at least a part of the pigment with a water-insoluble resin and forming a resin layer on the surface of the pigment is preferable. The use of an encapsulated pigment coated with such a water-insoluble resin is preferable from the viewpoint of the cohesiveness of the pigment, and is preferable in that a high-resolution image can be formed when recording at high speed.

Here, the phase inversion emulsification method will be described.
The phase inversion emulsification method is basically a self-dispersion (phase inversion emulsification) method in which a mixed melt of a resin having a self-dispersing ability or a dissolving ability and a pigment is dispersed in water. The mixed melt may contain a curing agent, a polymer compound or a curing agent. Here, the mixed molten material refers to a mixed state that is not dissolved, a state that is dissolved and mixed, or a state that includes both of these states. A more specific production method of the “phase inversion emulsification method” includes the method described in JP-A-10-140065.
For more specific methods of the above phase inversion emulsification method and acid precipitation method, the descriptions in JP-A-9-151342 and JP-A-10-140065 can be referred to.

~ Dispersant ~
The inkjet ink composition in the present invention can contain at least one dispersant. The pigment dispersant may be either a polymer dispersant or a low molecular surfactant type dispersant. The polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.

  “Water-insoluble” means that the amount of dissolution is 10 g or less when the dispersant is dried at 105 ° C. for 2 hours and then dissolved in 100 g of water at 25 ° C.

  The low molecular surfactant type dispersant can stably disperse the pigment in the aqueous solvent while keeping the ink at a low viscosity. The low molecular surfactant type dispersant is a low molecular dispersant having a molecular weight of 2,000 or less. The molecular weight of the low molecular surfactant type dispersant is preferably 100 to 2,000, and more preferably 200 to 2,000.

  The low molecular surfactant type dispersant has a structure including a hydrophilic group and a hydrophobic group. Moreover, the hydrophilic group and the hydrophobic group should just be independently contained 1 or more in 1 molecule, respectively, and may have multiple types of hydrophilic group and hydrophobic group. In addition, a linking group for linking a hydrophilic group and a hydrophobic group can be appropriately included.

  The hydrophilic group is anionic, cationic, nonionic, or a betaine type combining these. The anionic group may be any as long as it has a negative charge, but is preferably a phosphate group, phosphonic acid group, phosphinic acid group, sulfuric acid group, sulfonic acid group, sulfinic acid group or carboxylic acid group. More preferably a phosphoric acid group or a carboxylic acid group, and even more preferably a carboxylic acid group. The cationic group may be any as long as it has a positive charge, but is preferably an organic cationic substituent, and more preferably a nitrogen or phosphorus cationic group. Further, it is more preferably a pyridinium cation or an ammonium cation. Examples of the nonionic group include polyethylene oxide, polyglycerin, a part of sugar unit, and the like.

  The hydrophilic group is preferably an anionic group. The anionic group is preferably a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, or a carboxylic acid group, and more preferably a phosphoric acid group or a carboxylic acid group. Preferably, it is a carboxylic acid group.

The hydrophobic group has a hydrocarbon-based structure, a fluorocarbon-based structure, a silicone-based structure, or the like, and is particularly preferably a hydrocarbon-based structure. Further, the hydrophobic group may have a linear structure or a branched structure. Further, the hydrophobic group may have a single chain structure or a chain structure of more than this, and in the case of a structure of two or more chains, it may have a plurality of types of hydrophobic groups.
The hydrophobic group is preferably a hydrocarbon group having 2 to 24 carbon atoms, more preferably a hydrocarbon group having 4 to 24 carbon atoms, and further preferably a hydrocarbon group having 6 to 20 carbon atoms.

  Among polymer dispersants, water-soluble dispersants include hydrophilic polymer compounds. For example, natural hydrophilic polymer compounds include plant polymers such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, quince seed starch, seaweeds such as alginic acid, carrageenan and agar. Examples include molecules, animal polymers such as gelatin, casein, albumin and collagen, and microorganism polymers such as xanthene gum and dextran.

In addition, in hydrophilic polymer compounds modified from natural products, fiber polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starch such as sodium starch glycolate and sodium starch phosphate And seaweed polymers such as sodium alginate, propylene glycol alginate, and the like.
Further, synthetic hydrophilic polymer compounds include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamide, polyacrylic acid or alkali metal salts thereof, water-soluble styrene acrylic resins, and the like. Acrylic resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalene sulfonic acid formalin condensate, quaternary ammonium and amino And a polymer compound having a salt of a cationic functional group such as a group in the side chain, a natural polymer compound such as shellac, and the like.

  Among these, from the viewpoint of dispersion stability of the pigment, a polymer compound containing a carboxyl group is preferable. For example, an acrylic resin such as a water-soluble styrene acrylic resin, a water-soluble styrene maleic acid resin, a water-soluble vinyl naphthalene acrylic resin, A polymer compound containing a carboxyl group such as a water-soluble vinyl naphthalene maleic resin is particularly preferable.

  Among the polymer dispersants, as the water-insoluble dispersant, a polymer having both a hydrophobic portion and a hydrophilic portion can be used. For example, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, polyethylene glycol ( Examples thereof include (meth) acrylate- (meth) acrylic acid copolymers, vinyl acetate-maleic acid copolymers, and styrene-maleic acid copolymers.

  The weight average molecular weight of the polymer dispersant is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, still more preferably 5,000 to 80,000, and particularly preferably 10,000 to 60. , 000.

  From the viewpoint of self-dispersibility, the polymer dispersant preferably contains a polymer having a carboxyl group, preferably a polymer having a carboxyl group and an acid value of 100 mgKOH / g or less, and an acid value of 25 to 100 mgKOH. / G polymer is more preferred.

  Further, the mixing mass ratio of the pigment and the dispersant (pigment: dispersant) is preferably in the range of 1: 0.06 to 1: 3, more preferably in the range of 1: 0.125 to 1: 2. Preferably it is 1: 0.125 to 1: 1.5.

In the present invention, a resin-coated pigment in which at least a part of the pigment surface is coated with a crosslinked polymer obtained by crosslinking a water-soluble resin with a crosslinking agent is more preferable. The water-soluble resin acts as a dispersant for dispersing the pigment. When the pigment is coated with a cross-linked polymer, the pigment dispersion or an ink-jet ink composition using the pigment dispersion has excellent stability (stability against pH fluctuation, stability against temperature fluctuation). Can be granted. Examples of the water-soluble resin include polyvinyls, polyurethanes, polyesters, etc. Among them, polyvinyls are preferable.
The water-soluble resin referred to here has a group that causes a crosslinking reaction in the molecule by a crosslinking agent. Such a group is not particularly limited, and examples thereof include a carboxyl group or a salt thereof, an isocyanate group, and an epoxy group. In this invention, it is preferable to have a carboxyl group or its salt from a viewpoint of a dispersibility improvement.

The water-soluble resin is preferably a copolymer obtained using a carboxyl group-containing monomer as a copolymerization component. Examples of the carboxyl group-containing monomer include methacrylic acid, β-carboxyethyl acrylate, fumaric acid, itaconic acid, maleic acid, crotonic acid, and the like. Among these, from the viewpoint of crosslinkability and dispersion stability, methacrylic acid and β-carboxyl. Ethyl acrylate is preferred. In addition to the carboxyl group-containing monomer, an arbitrarily selected hydrophilic monomer or hydrophobic monomer may be used as a copolymerization component. The hydrophilic monomer may be ionic or nonionic. The hydrophobic monomer is not particularly limited, but an alkyl methacrylate having 1 to 20 carbon atoms or an alkyl acrylate having 1 to 20 carbon atoms is preferable.
The water-soluble resin may be a random polymer or a block or graft polymer.

  The acid value of the water-soluble resin (mg number of KOH necessary for neutralizing 1 g of the water-soluble resin) is preferably 135 to 250 mg KOH / g from the viewpoint of the dispersibility and dispersion stability of the pigment. More preferably, it is 200 mgKOH / g, and 135-180 mgKOH / g is especially preferable.

  The method for synthesizing the polymer as the water-soluble resin is not particularly limited, but random polymerization of vinyl monomers is preferable from the viewpoint of dispersion stability.

As the cross-linking agent, a compound having two or more sites that cause a cross-linking reaction can be used. Among them, a bifunctional or higher functional epoxy compound is preferable in that it has excellent reactivity with a carboxyl group. Specific examples of the bifunctional or higher epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl. Examples include ether and polypropylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether and diethylene glycol diglycidyl ether are preferable.
The molar ratio of the crosslinking site of the crosslinking agent to the crosslinked site of the water-soluble resin is preferably 1: 1.1 to 1:10 from the viewpoint of the crosslinking reaction rate and the stability of the dispersion liquid after crosslinking. 1 to 1: 5 is more preferable, and 1: 1.1 to 1: 3 is most preferable.
The amount of the water-soluble resin with respect to the pigment is preferably 10 to 250% by mass, more preferably 10 to 200% by mass, further preferably 20 to 150% by mass, and particularly preferably 30 to 100% by mass.

A resin-coated pigment in which the pigment surface is coated with a cross-linked polymer obtained by cross-linking a water-soluble resin with a cross-linking agent can be obtained through a step of cross-linking with a cross-linking agent after dispersing the pigment using the water-soluble resin. As an example of a preferable preparation method, a method performed through the following steps (1) to (3) is shown.
(1) Dispersing step of dispersing the pigment and water-soluble resin in water or an aqueous solution of a polar solvent to obtain a pigment dispersion (2) Adding a crosslinking agent to the pigment dispersion obtained in (1) above and heating Cross-linking step to coat the pigment surface with the cross-linked polymer by cross-linking reaction (3) step of purifying the resin-coated pigment coated with the cross-linked polymer In addition to these steps, other steps are appropriately performed as necessary It may be provided. In the step (1), known solvents can be appropriately used as the polar solvent.

  Specific examples of pigments coated with a crosslinked polymer obtained by crosslinking a water-soluble resin with a crosslinking agent include Projet Yellow APD1000, Projet Magenta APD1000, Projet Cyan APD1000, and Projet Black APD1000 (all manufactured by FUJIFILM Imaging Colors). Preferably used.

A dye may be used in place of the pigment. In the case of using a dye, a dye held on a water-insoluble carrier can be used. As the dye, known dyes can be used without limitation. For example, the dyes described in JP-A No. 2001-115066, JP-A No. 2001-335714, JP-A No. 2002-249677 and the like are preferably used. . The carrier is not particularly limited as long as it is insoluble or hardly soluble in water, and can be selected from inorganic materials, organic materials, and composite materials thereof. Specifically, the carriers described in JP-A Nos. 2001-181549 and 2007-169418 are preferably used.
The carrier holding the dye (water-insoluble colored particles) can be used as an aqueous dispersion using a dispersant. As the dispersant, the above-described dispersants can be suitably used.

  In the present invention, it is preferable to contain a pigment and a dispersant from the viewpoint of scratch resistance and quality of an image, and an organic pigment and a polymer dispersant are included, and at least a part of the pigment surface is coated with the polymer dispersant. More preferably, it is contained as a water-dispersible pigment. Furthermore, the inkjet ink composition particularly includes an organic pigment and a polymer dispersant containing a carboxyl group, and a water-dispersible pigment in which at least a part of the pigment surface is coated with a polymer dispersant having a carboxyl group. preferable.

The average particle size of the pigment in the dispersed state is preferably 10 to 200 nm, more preferably 10 to 150 nm, and still more preferably 10 to 100 nm. When the average particle size is 200 nm or less, the color reproducibility is good, and the droplet ejection characteristics when droplets are ejected by the ink jet method are good. When the average particle size is 10 nm or more, light resistance is improved. Further, the particle size distribution of the color material is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. Two or more color materials having a monodisperse particle size distribution may be mixed and used.
Here, the average particle diameter of the pigment in the dispersed state indicates the average particle diameter in the ink state, but the same applies to the so-called concentrated ink dispersion in the previous stage before the ink is formed.

  The average particle diameter of the pigment in the dispersed state, and the average particle diameter and particle size distribution of the polymer particles described later are measured using dynamic light using a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso Co., Ltd.). It is obtained by measuring the volume average particle diameter by a scattering method.

You may use a pigment individually by 1 type or in combination of 2 or more types.
As content in the inkjet ink composition of a pigment, 1-25 mass% is preferable with respect to the total amount of ink from a viewpoint of image density, and 2-15 mass% is more preferable.

(Water-soluble organic solvent)
The ink-jet ink composition in the present invention contains water (and optionally the humectant described above) as a solvent and can contain a water-soluble organic solvent that does not correspond to the humectant described above. By containing the water-soluble organic solvent together with the polymer particles, the minimum image film temperature of the polymer particles can be kept low in the ink, and the discharge properties and the like can be kept good. Here, water-soluble means to dissolve 1% by mass or more in 20 ° C. water.
The water-soluble organic solvent in the present invention is a liquid compound having a vapor pressure of 1 Pa or higher at 25 ° C. and can be relatively easily volatilized.

  Examples of the water-soluble organic solvent constituting the inkjet ink composition include polyhydric alcohols (for example, 1,2,6-hexanetriol, trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene. Glycol, pentaethylene glycol, dipropylene glycol, 1,2-hexanediol, 1,2-pentanediol, 1,3-butanediol, 1,2-butanediol, 2-butene-1,4-diol, 2-ethyl -1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol Alkanediol, etc.), amides ( For example, 2-pyrrolidone, N-methylpyrrolidone, etc.), monoethers of polyhydric alcohols (diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, etc.), diethers of polyhydric alcohols ( Tetreethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.).

  The water-soluble organic solvent may contain at least one kind alone, or a plurality of kinds may be contained in the ink in combination.

(Surfactant)
The inkjet ink composition in the present invention preferably contains a surfactant. By containing a surfactant, the surface tension can be adjusted. The surfactant content can be adjusted so that the surface tension of the ink composition is in the range of 30 mN / m to 40 mN / m, more preferably in the range of 33 mN / m to 38 mN / m. The surface tension of the ink composition is measured under conditions of 25 ° C. by a plate method using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).
Specific examples of surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensates in hydrocarbons, Anionic surfactants such as polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl Nonionic surfactants such as amines, glycerin fatty acid esters and oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (manufactured by Air Products & Chemicals) and Olphine series (manufactured by Nissin Chemical Industry), which are acetylene-based polyoxyethylene oxide surfactants, are also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred.
Furthermore, pages (37) to (38) of JP-A-59-157636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.
Further, fluorine (fluorinated alkyl type) surfactants, silicone type surfactants and the like described in JP-A Nos. 2003-322926, 2004-325707, and 2004-309806 are disclosed. By using, the abrasion resistance can be improved.
Further, the surface tension adjusting agent can also be used as an antifoaming agent, and fluorine compounds, silicone compounds, chelating agents represented by EDTA, and the like can also be used.

(Other additives)
The ink-jet ink composition in the present invention may contain other additives as necessary in addition to the above-described components. Examples of other additives include antifading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, antiseptics, antifungal agents, pH adjusters, antifoaming agents, viscosity modifiers, dispersants, and dispersion stabilizers. And known additives such as rust preventives and chelating agents. These various additives may be added directly after the ink composition is prepared, or may be added when the ink composition is prepared.

  The ultraviolet absorber can improve the storage stability of the image. Examples of ultraviolet absorbers include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, JP-A-56-21141 Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent can improve the storage stability of the image. As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in Japanese Patent No. 15162 and the compounds included in the general formulas and compound examples of typical compounds described on pages 127 to 137 of JP-A-62-215272 can be used.

Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink composition in an amount of 0.02 to 1.00% by mass.
As the pH adjuster, a neutralizer (organic base, inorganic alkali) can be used. From the viewpoint of improving the storage stability of the ink composition, the pH adjuster is preferably added so that the ink composition has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10.
As the antifoaming agent, for example, a compound such as BYK series (BYK) such as BYK-024 can be preferably used.

(water)
The ink-jet ink composition in the present invention contains water, but the amount of water is not particularly limited. Among them, the amount of water is preferably 10% by mass or more and 99% by mass or less, and more preferably 20% by mass or more and 70% by mass with respect to the total mass of the inkjet ink composition from the viewpoint of ensuring stability and ejection reliability. It is below mass%.

-Recording substrate-
In the image forming method of the present invention, a recording substrate which is an aggregate of non-absorbing or low-absorbing fiber materials is used. The recording substrate refers to a recording material on which an image is recorded by an ink jet method.

Non-absorptivity or low absorptivity indicates the degree of absorption of the ink-jet ink composition of the recording substrate, but since the ink is water-based, it can be evaluated by water absorbency as described below. That is,
In the present invention, “non-absorbable fiber” means a fiber having a composition having a water absorption (mass%, 24 hr.) Of less than 0.2 according to ASTM D570 of ASTM test method. The term “fiber” refers to a fiber having a composition having a water absorption (mass%, 24 hr.) Of 0.2 or more and less than 0.5 according to ASTM D570 of the ASTM test method.

  Examples of non-ink-absorbing or low-absorbing fiber materials include polyolefin fibers (for example, fibers such as polypropylene and polyethylene), polyester fibers (for example, fibers such as polyethylene terephthalate and polyethylene naphthalate), aramid fibers, and cellulose fibers. And synthetic fibers such as nylon fiber, vinylon fiber and rayon fiber, metal fibers such as stainless steel, iron, gold, silver and aluminum, and glass fibers (glass wool and the like).

  Examples of aggregates of non-ink-absorbing or low-absorbing fiber materials include non-woven fabrics, woven fabrics, and glass wool.

  Non-woven fabric refers to a sheet-like entangled fiber without woven, and includes hydroentangled non-woven fabric. Nonwoven fabrics are processed sheets, webs, or bats of fibers that are oriented in one direction or randomly and are secured by friction, adhesion, adhesion, or the like. Nonwovens do not include woven or knitted, or tufted, stitchbonded incorporating thread or filament bonds, or felted by wet milling.

  In the present invention, among the above, the nonwoven fabric is preferable, more preferable because it is low in cost, processability, and is relatively weak in scratch resistance of an image and easily causes bleeding, and the effects of the present invention are more exerted. Is a nonwoven fabric of polyolefin fibers.

  In the recording base material of the present invention, the diameter (fiber diameter) of the cross section perpendicular to the fiber axis direction of the fibers constituting the recording base material is preferably 1 μm to 200 μm, more preferably 1 μm to 100 μm, and particularly preferably. 5 μm to 60 μm. A fiber diameter of 1 μm or more is advantageous in terms of image abrasion resistance and stiffness of the recording substrate itself, and a fiber diameter of 200 μm or less is advantageous in terms of image bleeding and texture of the recording substrate.

  The thickness of the recording substrate is preferably 1 μm to 1000 μm, more preferably 1 μm to 800 μm, still more preferably 5 μm to 500 μm, and particularly preferably 5 μm to 300 μm. The thickness of 1 μm or more is advantageous in terms of stiffness of the recording substrate itself, and the thickness of 1000 μm or less is advantageous in terms of texture of the recording substrate.

The density of the recording substrate (fiber areal ^density), preferably from ^{1g / m 2 ~300g / m 2} , more preferably ^{1g / m 2 ~200g / m 2} , 5g / m 2 ~100g / m 2 is particularly preferred . A fiber surface density of 1 g / m ² or more is advantageous in that an image density can be easily obtained, and a fiber surface density of 300 g / m ² or less is advantageous in terms of image abrasion resistance and image bleeding.
The fiber surface density is the ratio [g / m ² ] of the amount of fibers present on the surface to the area of the surface where the fibers are distributed two-dimensionally, and the recording substrate is cut out in unit area. This is the value obtained by measuring the weight.

  The recording substrate may be formed by any method such as melt blowing, spun bonding, solvent spinning, electrospinning, carding and the like.

  Prior to the ink application step, a pretreatment step for pretreatment by subjecting the recording substrate to a hydrophilic treatment may be provided. By carrying out the hydrophilic treatment, it is possible to prevent ink repellency adjusted to a water system, and to adhere the ink onto the fiber, specifically, the direction in which the fiber extends, that is, the ink region that adheres in the fiber axis direction, is secured. The scratch resistance of the image can be further improved.

Examples of the hydrophilic treatment include, but are not limited to, corona treatment, plasma treatment, flame treatment, heat treatment, wear treatment, light irradiation treatment (UV treatment), and flame treatment. For example, when the surface of the recording substrate is subjected to corona treatment in advance before recording an image by applying the inkjet ink composition, the surface energy of the substrate is increased, and the substrate surface is wetted and applied to the substrate. Adhesion can be promoted. The corona treatment can be performed using, for example, a corona master (manufactured by Shinko Electric Meter Co., Ltd., PS-10S). The conditions for the corona treatment may be appropriately selected depending on the case, such as the type of the recording substrate and the ink composition. For example, the following processing conditions may be used.
・ Processing voltage: 10 to 15.6 kV
・ Processing speed: 30 to 100 mm / s
As the hydrophilization treatment in the present invention, a mode in which corona treatment is performed is preferable from the viewpoint of cost and workability.

The surface tension of the recording substrate is preferably 3.4 × 10 ⁻⁶ J to 4.5 × 10 ⁻⁶ J (about 34 to 45 dynes / cm), and 3.5 × 10 ⁻⁶ J to 4 0.0 × 10 ⁻⁶ J (about 35 to 40 dynes / cm) is more preferable. If the surface tension of the substrate is too small, the adhesion of the image may decrease, and if the surface tension of the substrate is too large, the texture of the recording substrate itself may decrease. In addition, the surface tension of a base material can measure the liquid mixture number which a base material begins to get wet with the liquid mixture for a wetting tension test (made by Wako Pure Chemical Industries Ltd.) as a surface tension of a base material.
In this case, the surface tension of the ink is preferably in the range of 20 mN / m to 40 mN / m, and is appropriately selected from the above range in order to adjust the average length of the ink attached in the fiber axis direction described later. be able to. The surface tension of the ink is measured by the Wilhelmi method using a static surface tension measuring device (for example, TD3 manufactured by Ikeda Rika Co., Ltd.).

<Light irradiation process>
The image forming method of the present invention is preferably configured by providing a light irradiation step for irradiating an image formed by applying an inkjet ink composition onto a recording substrate in the ink application step described above. .

  Examples of the light irradiated in the light irradiation step in the present invention include ultraviolet rays (UV light).

  Although the peak wavelength of UV light depends on the absorption characteristics of the sensitizing dye used as necessary, it is preferably, for example, 200 nm to 405 nm, more preferably 220 nm to 390 nm, and 220 nm to 350 nm. More preferably. When the ink composition of the present invention does not contain a sensitizing dye or a photopolymerization initiator, the peak wavelength of UV light is preferably 200 nm to 310 nm, and more preferably 200 nm to 280 nm.

UV light, illuminance of the exposure surface is, for ^{example, 10mW / cm 2 ~2000mW / cm} 2, ^preferably, may be irradiated so that ^{20mW / cm 2 ~1000mW / cm 2} .

  As the UV light source, a mercury lamp, a gas laser, a solid laser, or the like is mainly used, and a mercury lamp, a metal halide lamp, and a UV fluorescent lamp are widely known. In addition, replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally, and LED (UV-LED) and LD (UV-LD) are small in size, have a long lifetime, high efficiency, and Low cost and expected as a UV light source. When the ink composition of the present invention contains a sensitizing dye or a photopolymerization initiator, a metal halide lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, or a UV-LED is preferable, and the ink composition of the present invention. Is free of a sensitizing dye or a photopolymerization initiator, a medium pressure mercury lamp or a low pressure mercury lamp is preferred, and a low pressure mercury lamp is particularly preferred.

In the light irradiation step, the inkjet ink composition applied to the recording medium, that is, the image is irradiated with light such as UV light, for example, for 0.01 seconds to 120 seconds (preferably 0.1 seconds to 90 seconds). It is preferable to do. The light irradiation is suitably performed after a certain period of time (for example, 0.01 seconds to 120 seconds, preferably 0.01 seconds to 60 seconds) after the ink has landed on the recording medium and dried by heating.
Regarding the light irradiation conditions and irradiation method, the irradiation conditions and irradiation method disclosed in JP-A-60-132767 can be similarly applied to the present invention. Specifically, a light source is provided on both sides of the head unit including the ink ejection device, and a method of scanning the head unit and the light source by a so-called shuttle method or a method of irradiating with another light source that is not driven is preferable.

<Drying process>
In the present invention, the ink applied to the recording substrate is dried during the application of the inkjet ink composition in the ink application process and / or after the application of the inkjet ink composition and before or after the light irradiation process. A drying step is preferably provided. At this time, an image (ink) may be dried and a drying and fixing process may be performed in which the image is heated and fixed on the recording substrate.

Through the drying process, the evaporation of the liquid medium in the ink (specifically, water and water-soluble organic solvent) is promoted, resulting in high-quality images with little unevenness and blurring and excellent scratch resistance. Things can be obtained in a short time. At this time, by further containing the above-described moisturizing agent such as a polyhydric alcohol compound, the flexibility and flexibility of the cured image and the drapability are improved.
Further, the occurrence of wrinkles on the recording base material can be prevented, and further the curling of the recording base material can be prevented.
Further, when a drying and fixing step for heat-fixing an image at the time of drying is provided, the heating may promote the fusion of polymer particles contained in the ink composition to form a film. This further improves the scratch resistance of the image.

The drying temperature at the time of drying is not particularly limited as long as the liquid medium present in the ink evaporates and a film formed of polymer particles is formed. Among these, the drying temperature is preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 40 ° C. or higher and 80 ° C. or lower. When the temperature is 80 or less, deformation of the recording substrate can be prevented.
The heating time at the time of drying is not particularly limited as long as the liquid medium in the ink evaporates and a film can be formed with the polymer particles, and is appropriately determined in consideration of the liquid medium type, the polymer type, the recording speed, and the like. You can choose.

  The drying method is not particularly limited as long as it is a method for promoting the volatilization of the liquid medium contained in the ink. Examples of the drying method include a method of applying heat to the recording base material before and after recording, a method of blowing air on the recording base material after recording, or a method combining these. Specific examples include forced air heating, radiation heating, conduction heating, high frequency drying, microwave drying, and dry air blowing.

-Image recordings-
In the image forming method of the present invention, a recording base material that is an aggregate of non-absorbing or low-absorbing fiber materials, an uncured polymer derived from polymer particles provided on the recording base material, and water-soluble photocuring An image recorded matter composed of an image containing a cured polymer derived from a conductive polymer is obtained. This recorded image is formed using polymer particles and a water-soluble photocurable polymer, so that it has excellent scratch resistance while maintaining the adhesion of the ink image to the recording substrate. Has a good drape.

Details of the recording substrate, the polymer particles forming the ink image, the water-soluble photocurable polymer, and the like are as described above.
The polymer is the same as the polymer constituting the polymer particles described above. The polymer here may be contained in the form of polymer particles, or may be contained in a form different from the particles.

  The thickness of the ink image is not particularly limited, but is preferably 0.1 μm to 10.0 μm. When the thickness is within the above range, it is advantageous in terms of scratch resistance, adhesion and image texture.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC). GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as a column, and THF (tetrahydrofuran) as an eluent. Was used.

Example 1
-Preparation of inkjet ink-
Each component in the composition shown below was mixed to prepare an ink. After preparation, this ink was packed in a plastic disposable syringe and filtered through a polyvinylidene fluoride (PVDF) pore size 5 μm filter (Millex-SV, Millipore, diameter 25 mm) to obtain a magenta ink.
<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether
・ Orphine E1010 ・ ・ ・ 1 part (Acetylene glycol surfactant; manufactured by Nissin Chemical Industry Co., Ltd.)
WBR-016U 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C., volume average particle size: about 30 nm))
-The following polymer P-1 (17% polymer solid concentration solution) ... 29.4 parts (water-soluble photocurable polymer having a structure represented by the general formula (1))
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

  Said polymer P-1 was synthesize | combined with reference to Unexamined-Japanese-Patent No. 52-988 and Unexamined-Japanese-Patent No. 2009-138172.

-Image recording and evaluation-
1. Image recording With respect to a polypropylene nonwoven fabric (fiber surface density: 30 g / m ² , thickness: 13 μm, fiber diameter: 20 μm), using a corona master (manufactured by Shinko Electric Meter Co., Ltd., PS-10S), processing voltage: 14 kV, processing Speed: Corona treatment was performed twice under the condition of 50 mm / sec. The magenta ink was ejected to the nonwoven fabric subjected to the corona treatment with an ink droplet amount of 85 pl using a head Polaris 512/85 manufactured by Fujifilm Dimatix, and a 100% solid image of 200 dpi was recorded (ink application process) ). This solid image was brought into intimate contact with a nylon mesh platform, and dried from the non-image-forming surface side of the nonwoven fabric with a dryer at a wind speed of 7 m / s and a temperature of 40 ° C. for 120 seconds (drying process).
Subsequently, the solid image was exposed with a low-pressure mercury lamp under the condition that the irradiation energy was 500 mJ / cm ² (light irradiation step). In this way, an image sample was obtained.

2. Evaluation (2-1) Image Abrasion Resistance The image part of the obtained image sample was moistened with 0.05 mL of water using a Gakushin friction tester (No. 428, manufactured by Yasuda Seiki Co., Ltd.). By rubbing white cotton (wet area about 20 mm x about 20 mm) with a force of about 2 N and rubbing for a specified number of reciprocations, the color transferred to the white cotton is visually scratch-resistant according to the following evaluation criteria. evaluated. Among the evaluation criteria, “A to B” is an allowable range.
<Evaluation criteria>
A: Even when the white cotton was reciprocated 10 times and the image area was rubbed, the color transfer to the white cotton was slight.
B: When white cotton was reciprocated 10 times and the image portion was rubbed, a slight color transfer was observed on the white cotton, but there was no practical problem.
C: When white cotton is reciprocated 10 times and the image area is rubbed, color transfer is observed in white cotton, which impedes practical use.
D: When white cotton is reciprocated twice and the image portion is rubbed, noticeable color transfer is observed in white cotton.

(2-2) Drapability Based on JIS L 1096, the drape coefficient was measured by a drape tester, and the stiffness of the image sample (polypropylene nonwoven fabric with an image) was evaluated using the measured value as an index. Specifically, with respect to the image sample obtained as described above, a drape coefficient was measured using a drape tester (manufactured by Daiei Kagaku Seisakusho Co., Ltd.) and evaluated according to the following evaluation criteria. Here, evaluation is made including the texture of the image (hardness and softness of the image). In addition, the drape coefficient of the used base material itself evaluated with the thing of 0.4-0.6.
<Evaluation criteria>
A: The difference between the drape coefficient of the image sample and the drape coefficient of the substrate itself is less than 0.2, and the texture of the image is also good.
B: The difference between the drape coefficient of the image sample and the drape coefficient of the substrate itself is 0.2 or more and less than 0.3, and there is no practical problem as the texture of the image.
C: The difference between the drape coefficient of the image sample and the drape coefficient of the base material itself is 0.3 or more and less than 0.4, which is slightly inferior as the texture of the image.
D: The difference between the drape coefficient of the image sample and the drape coefficient of the substrate itself is 0.4 or more, and the texture of the image is poor.

(Example 2)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-2101 ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 40 ° C, volume average particle size: about 30 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Sanix GP-250 ... 5 parts (manufactured by Sanyo Chemical Industries; vapor pressure (25 ° C): less than 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 3)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part Aron HD-5 16.7 parts (manufactured by Toa Gosei Co., Ltd., 30% by weight dispersion of acrylic resin fine particles (Tg: 45 ° C., volume average particle size: about 10 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

Example 4
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · Johncrill 741 ... 10.2 parts (manufactured by Johnson Polymer Co., Ltd., 49% by mass dispersion of styrene / acrylic resin fine particles (Tg: 15 ° C, volume average particle diameter: about 100 nm)) )
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 5)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Diglycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): less than 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 6)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Urea (manufactured by Tokyo Chemical Industry Co., Ltd .; vapor pressure (25 ° C.): 80 Pa) ・ ・ ・ 5 parts ・ BYK-024 (antifoaming agent, manufactured by BYK Chemie) ・ ・ ・ 0.1 part Remaining amount when the total amount is 100 parts (parts)

(Example 7)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.) 5 parts ・ BYK-024 (Antifoamer, manufactured by BYK Chemie) ・ 0.1 parts ・ Ion exchange water Remaining part (part)

(Example 8)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

Example 9
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-The following polymer P-2 (polymer solid concentration 17% solution) ... 29.4 parts (water-soluble photocurable polymer having a structure represented by the general formula (1))
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

  The polymer P-2 was synthesized with reference to Japanese Patent Application Laid-Open Nos. 52-988 and 2009-138172.

(Example 10)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-The following polymer P-3 (17% polymer solid concentration solution) ... 29.4 parts (water-soluble photocurable polymer having a structure represented by the general formula (1))
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

  The above polymer P-3 was synthesized with reference to JP-A-52-988 and JP-A-2009-138172.

(Example 11)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
O-106 (manufactured by Chukyo Yushi Co., Ltd .; aqueous photocurable polymer) 5 parts (solid content)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 12)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.
<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-2101 ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 40 ° C, volume average particle size: about 30 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 13)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.
<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-2108 1s 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 0 ° C, volume average particle size: about 30 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 14)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.
<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part ・ UW-5101-E 16.7 parts (manufactured by Ube Industries, 30% by mass dispersion of polyurethane fine particles (Tg: 69 ° C., volume average particle size: about 35 nm))
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 15)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.
<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part Dispersal U-53 12.5 parts (manufactured by Sumika Bayer, 40% by mass dispersion of polyurethane fine particles (Tg: −58 ° C., volume average particle size: about 154 nm)) liquid)
-Said polymer P-1 ... 29.4 parts (Polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 16)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.
<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part / WBR-016U 31.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by weight dispersion of polyurethane fine particles (Tg: 20 ° C., volume average particle size: about 30 nm))
-Above-mentioned polymer P-1 ... 2.9 part (Polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 17)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.
<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U 6.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-Said polymer P-1 ... 47.1 parts (polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Example 18)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.
<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 30 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-Above-mentioned polymer P-1 ... 5.9 part (Polymer solid content concentration 17 mass% solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Comparative Example 1)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Comparative Example 2)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) 1 part · WBR-016U ... 16.7 parts (manufactured by Taisei Fine Chemical Co., Ltd., 30% by mass dispersion of polyurethane fine particles (Tg: 20 ° C, volume average particle size: about 30 nm))
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Comparative Example 3)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) (Made by company) ... 1 part of the above-mentioned polymer P-1 ... 29.4 parts (polymer solid concentration 17% by mass solution)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

(Comparative Example 4)
A magenta ink was prepared and evaluated in the same manner as in Example 1 except that the composition of the inkjet ink was changed to the following composition.

<Magenta ink composition>
Projet Magenta APD1000: 28.57 parts (manufactured by FUJIFILM Imaging Colorants, magenta pigment dispersion, pigment concentration: 14%)
・ 2-Pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 12 parts ・ Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ ・ ・ 2 parts ・ Tripropylene glycol monomethyl ether ・ ・ ・ 2 parts ・ Orphine E1010 (Nisshin Chemical Industries) (Made by company) ... 1 part of the above-mentioned polymer P-1 ... 29.4 parts (polymer solid concentration 17% by mass solution)
・ Glycerin: 5 parts (manufactured by Tokyo Chemical Industry; vapor pressure (25 ° C.): 0.01 Pa)
-BYK-024 (antifoaming agent, manufactured by Big Chemie) ... 0.1 part-Ion-exchanged water ... Residue when the total amount of ink is 100 parts (parts)

  As shown in Table 2, in the examples, the image was excellent in scratch resistance and good drapeability could be imparted. On the other hand, in the comparative example in which the photocurable polymer and the polymer particles are not used in combination, it is difficult to achieve both scratch resistance and drape properties, which are mutually contradictory properties.

The present invention can be applied to any application for recording an image on a non-absorbing or low-absorbing recording substrate. For example, it is suitable for uses (such as diapers (including disposable pants), training pants, and hygiene articles such as adult incontinence underwear) that use a nonwoven fabric as a non-absorbent or low-absorbent recording substrate.
The above-mentioned “diaper” refers to an absorbent article generally worn around the lower torso so as to surround the waist and legs of a wearer by an infant or a person with incontinence symptoms and can receive urine, defecation, etc. .

Claims (11)

  An ink for applying an ink-jet ink composition containing at least polymer particles, a water-soluble photocurable polymer, and water onto a recording substrate that is an aggregate of non-absorbing or low-absorbing fiber materials by an ink-jet method An image forming method having an applying step.   The image forming method according to claim 1, wherein the inkjet ink composition further contains a compound selected from the group consisting of a polyhydric alcohol compound, an amide compound, and an amine compound. The image forming method according to claim 1, wherein the photocurable polymer has a partial structure represented by the following general formula (1).

[In General Formula (1), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R ^a and R ^b is alkyl having 1 to 4 carbon atoms. Represents a group. R ^a and R ^b may be bonded to each other to form a 4- to 6-membered alicyclic structure. “*” Represents a binding site with a main chain or a side chain in the polymer. ] The image forming method according to claim 1, wherein the photocurable polymer has a repeating unit represented by the following general formula (2).

[In General Formula (2), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R ^a and R ^b is alkyl having 1 to 4 carbon atoms. Represents a group. R ^a and R ^b may be bonded to each other to form a 4- to 6-membered alicyclic structure. R ^c represents a hydrogen atom or a methyl group. Z represents a single bond, —COO — ^** or —CONR ^d — ^** , R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and “**” represents a bonding position with X. . X represents an alkylene group or an aralkylene group. ]   The image forming method according to any one of claims 1 to 4, wherein the polymer particles have a glass transition temperature (Tg) of -60C to 70C.   The image forming method according to claim 1, wherein the polymer particles are particles containing a resin selected from the group consisting of a urethane resin, an acrylic resin, and a styrene resin.   The image forming method according to claim 2, wherein the compound selected from the group consisting of the polyhydric alcohol compound, the amide compound, and the amine compound has a vapor pressure at 25 ° C. of less than 1 Pa. .   The total content of the compound selected from the group consisting of the polyhydric alcohol compound, the amide compound, and the amine compound is in the range of 1% by mass to 15% by mass with respect to the total mass of the inkjet ink composition. The image forming method according to any one of claims 2 to 7.   The image according to any one of claims 1 to 8, further comprising a light irradiation step of irradiating an image formed by applying an ink jet ink composition onto a recording substrate in the ink application step. Forming method.   10. The image forming method according to claim 1, wherein in the ink application step, the ink-jet ink composition is applied to a recording substrate with an ink droplet amount of 30 pl to 120 pl. The ratio (P / CP) of the content (P) of the polymer particles to the content (CP) of the photocurable polymer is in the range of 9.5 / 0.5 to 2/8 by mass ratio. The image forming method according to claim 10.