JP5885968B2 - Black ink composition, ink set, and image forming method - Google Patents

Description

  The present invention relates to a black ink composition, an ink set, and an image forming method.

  Inkjet technology has been applied as an image recording method for recording color images in the fields of office printers, home printers, and the like. A pigment is widely used as a colorant for an ink component used in inkjet, and carbon black is often used for black ink.

In an ink composition using a carbon black pigment, the hue of the black ink can be improved by using a color pigment in addition to the carbon black pigment (see, for example, Patent Document 1).
Also, ultraviolet curable pigment inks have been developed as inks for inkjet recording (see, for example, Patent Documents 2 and 3). The ultraviolet curable pigment ink basically includes a pigment, a polymerizable compound, and a polymerization initiator. When the ultraviolet curable pigment ink is black, a carbon black pigment is generally used as the pigment.

Japanese Patent No. 3859109 JP 2004-027211 A JP 2005-178331 A

However, in the case of an aqueous ink containing a carbon black pigment, a polymerizable compound, and a polymerization initiator, adhesion and rubbing resistance may be lowered or hue variation may be increased in the formed image.
The present invention has been made in view of the above, and it is an object of the present invention to provide a black ink composition, an ink set, and an image forming method capable of forming an image with suppressed hue variation and excellent adhesion and abrasion resistance. And

  The present inventor contains at least one color pigment selected from a magenta pigment and a cyan pigment in a black ink composition containing a carbon black pigment, a polymerizable compound, a polymerization initiator, and water, and By specifying the average primary particle size of the carbon black pigment, the content ratio of the carbon black pigment in the total pigment, and the total amount of the total pigment in the ink composition, the hue variation of the image is suppressed, and the adhesion and resistance of the image are reduced. The knowledge that the rubbing property is improved was obtained, and the present invention was completed based on this knowledge.

That is, specific means for solving the above problems are as follows.
<1> An average of the carbon black pigment, comprising a carbon black pigment, at least one color pigment selected from a magenta pigment and a cyan pigment, a water-soluble polymerizable compound, a polymerization initiator, and water. The primary particle diameter is 35 nm or more, the content ratio of the carbon black pigment is 60% by mass or more and 90% by mass or less with respect to the total amount of all pigments, and the total amount of all pigments is with respect to the total amount of the black ink composition. A black ink composition for ink-jet recording having a content of 1.5% by mass or more and 4% by mass or less.
<2> The black ink composition according to <1>, wherein at least a part of the surface of the carbon black pigment and the at least one color pigment is coated with a resin having a salt-forming group.
<3> The black ink composition according to <1> or <2>, wherein the water-soluble polymerizable compound includes a polyfunctional polymerizable compound and a monofunctional polymerizable compound having a (meth) acrylamide structure.
<4> The black ink composition according to <2> or <3>, wherein the resin having a salt-forming group is crosslinked by a crosslinking agent.
<5> The black ink composition according to any one of <2> to <4>, wherein the resin having a salt-forming group has at least one of an aromatic ring structure and an alicyclic structure.

<6> The black ink composition according to any one of <1> to <5>, wherein the polymerization initiator is a compound represented by the following general formula (1).

[In General Formula (1), m and n each independently represent an integer of 0 or more, and m + n represents an integer of 0 to 3. ]

<7> The black ink composition according to any one of <1> to <6>, further including an acetylene glycol surfactant.
<8> The black ink composition according to any one of <1> to <7>, wherein the total amount of all pigments is 1.8% by mass or more based on the total amount of the black ink composition .
< 9 > The black ink composition according to any one of <1> to < 8 >, wherein the carbon black pigment has a DBP absorption amount of 50 ml / 100 g or more and 150 ml / 100 g or less.

< 10 > The black ink composition according to any one of <1> to < 9 >, and a treatment liquid containing an aggregating agent capable of forming an aggregate by contact with the black ink composition; An ink set for ink-jet recording, comprising:
< 11 > The ink set according to < 10 >, wherein the flocculant is an acidic compound.

< 12 > An ink set according to < 10 > or < 11 > is used, and a treatment liquid application step for applying the treatment liquid to a recording medium; and an ink application step for applying the black ink composition to the recording medium; An image forming method comprising: a curing step of irradiating the image formed by the treatment liquid applying step and the ink applying step with active energy rays to cure the image.

  According to the present invention, it is possible to provide a black ink composition, an ink set, and an image forming method capable of forming an image with suppressed hue variation and excellent adhesion and abrasion resistance.

Hereinafter, although the form for implementing this invention is demonstrated in detail, this invention is not limited to this, A various deformation | transformation can be implemented within the range of the meaning.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

≪Black ink composition≫
The black ink composition of the present invention (hereinafter also simply referred to as “ink composition” or “ink”) is a black ink composition for ink jet recording, and is selected from a carbon black pigment, a magenta pigment, and a cyan pigment. At least one color pigment, a water-soluble polymerizable compound, a polymerization initiator, and water, and the carbon black pigment has an average primary particle size of 35 nm or more, and the carbon black pigment is contained. The ratio is 60% by mass or more with respect to the total amount of all pigments, and the total amount of all pigments is 4% by mass or less with respect to the total amount of the black ink composition.
According to the ink composition of the present invention, hue variation is suppressed, and an image excellent in adhesion to a recording medium and excellent in abrasion resistance can be formed.
The reason why such an effect is obtained is presumed as follows.

Generally, when a carbon black pigment is contained in an ink composition containing a polymerizable compound, a polymerization initiator, and water, the carbon black pigment tends to inhibit polymerization (curing). This is because carbon black pigment has higher absorbance in the short wavelength region (for example, ultraviolet region) than that in the longer wavelength region than the short wavelength region, and the carbon black pigment adsorbs radicals. This is because it is easy.
However, as a result of studies by the present inventors, it has been found that the absorbance in the short wavelength region decreases as the average primary particle size of the carbon black pigment increases.
Therefore, in the ink composition of the present invention, when the average primary particle diameter of the carbon black pigment is 35 nm or more, the polymerization inhibition effect by the carbon black pigment is reduced. As a result, in an image formed using the ink composition, curing in the thickness direction (depth direction) is promoted, and adhesion to the recording medium is improved. In addition, since the polymerization inhibitory effect by the carbon black pigment is reduced, the abrasion resistance of the image is also improved.

Further, according to the study of the present inventors, when the ink composition contains a carbon black pigment having an average primary particle diameter of 35 nm or more and at least one color pigment selected from a magenta pigment and a cyan pigment. It was found that if the content of the carbon black pigment is too small, the hue variation of the image tends to increase.
In this regard, in the ink composition of the present invention, the content ratio of the carbon black pigment having an average primary particle diameter of 35 nm or more is 60% by mass or more with respect to the total amount of all pigments, whereby the hue variation of the image. Is suppressed.
Here, the hue variation refers to a phenomenon in which the hue changes with the change of the halftone dot density when the halftone dot density of the image is changed.
If the hue variation is large, the desired black color with little yellowness or the intermediate color tone with little yellowness (such as gray color tone) may not be obtained.

  Further, in the ink composition of the present invention, the total amount of all pigments is 4% by mass or less with respect to the total amount of the black ink composition, thereby improving the adhesion of the image to the recording medium and the image abrasion resistance. To do.

  As described above, according to the ink composition of the present invention, hue variation is suppressed, and an image excellent in adhesion to a recording medium and excellent in abrasion resistance can be formed.

<Carbon black pigment>
The black ink composition of the present invention contains at least one carbon black pigment.
As described above, the average primary particle size of the carbon black pigment is 35 nm or more.
When the average primary particle diameter is less than 35 nm, the adhesion and rubbing resistance (particularly adhesion) of the image are lowered. Further, when the average primary particle diameter is less than 35 nm, the hue variation of the image becomes large.
In the present invention, the average primary particle size is a particle size (area) of 1000 primary particles arbitrarily selected from an image taken using a transmission electron microscope TEM2010 (pressurized voltage 200 kV) manufactured by JEOL Ltd. The equivalent circle diameter) is measured and calculated as the arithmetic average. That is, the average primary particle diameter of the present invention represents the arithmetic average particle diameter of the equivalent area circle diameter.

  The average primary particle diameter of the carbon black pigment is preferably 35 nm to 70 nm, more preferably 35 nm to 60 nm, and particularly preferably 40 nm to 60 nm, from the viewpoint of further suppressing hue fluctuation.

  In the black ink composition of the present invention, the volume average secondary particle diameter of the carbon black pigment is not particularly limited, but is preferably 70 nm to 170 nm from the viewpoint of hue. The volume average secondary particle diameter can be measured with a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.).

The DBP absorption amount of the carbon black pigment is not particularly limited, but is preferably 30 ml / 100 g or more and 200 ml / 100 g or less, and more preferably 50 ml / 100 g or more and 150 ml / 100 g or less from the viewpoint of color tone and printing density. .
The DBP absorption is measured by the JIS K6221 A method.

Also, the carbon black BET specific surface area of the pigment is not particularly limited, from the viewpoint of printing density and storage stability, is preferably not more than ^{30 m} 2 / g or more ^{450m 2 / g, 200m 2 /} g or more 400 meters ² / g The following is more preferable.

Examples of the carbon black pigment include those produced by known methods such as a contact method, a furnace method, and a thermal method.
Specific examples include, for example, Raven 860 Ultra, Raven 520, Raven 500, Raven 450, Raven 460, Raven 415, Raven 14, Conductex 7055 Ultra (or Colombian Carbon), Regal 99, Regal 350, MONARCH 280, MONARCH 280 Printex 200, Printex A, Printex G, Special Black 250, Special Black 100, NEROX 1000, NEROX 2500 (above, manufactured by Evonik Degussa), No. 10, no. 20, no. 25, no. 95, no. 85, no. 260, MA220 (manufactured by Mitsubishi Chemical Corporation), and the like. However, it is not limited to these.

The above carbon black pigments may be used singly or in combination of two or more.
The content ratio of the carbon black pigment in the ink composition of the present invention (the total content ratio in the case of 2 or more types) is not particularly limited, but is 0.5 to 4 from the viewpoint of more effectively achieving the effects of the present invention. It is preferable that it is mass%, and it is more preferable that it is 0.8-3.5 mass%.

<Coloring pigment>
The ink composition of the present invention contains at least one color pigment of a magenta pigment and a cyan pigment in addition to the carbon black pigment.
The magenta pigment and the cyan pigment can be appropriately selected from known organic pigments according to the purpose. Specific examples of the organic pigment used in the present invention are shown below.

Examples of magenta pigments include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 222, C.I. I. Pigment violet 19 and the like.
Among these, from the viewpoints of adhesion and abrasion resistance, C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. It is preferably at least one selected from pigment violet 19.

Examples of cyan pigments include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment Green 7, and siloxane-crosslinked aluminum phthalocyanine described in US Pat. No. 4,311,775.
Among these, from the viewpoints of adhesion and abrasion resistance, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. preferably at least one selected from CI Pigment Blue 16. I. Pigment blue 15: 3, C.I. I. More preferably, it is at least one selected from CI Pigment Blue 15: 4.

The ink composition of the present invention may contain at least one yellow pigment as required in addition to at least one magenta pigment and cyan pigment.
Examples of the yellow pigment include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. And CI Pigment Yellow 185.
Among these, from the viewpoints of adhesion and abrasion resistance, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 155, C.I. I. It is preferably at least one selected from Pigment Yellow 185.

  In the present invention, it is preferable that at least one magenta pigment and at least one cyan pigment are included as colored pigments from the viewpoint of suppression of hue variation and improvement of adhesion and abrasion resistance.

In the present invention, the content ratio of the carbon black pigment is 60% by mass or more based on the total amount of all the pigments. When the content ratio of the carbon black pigment is less than 60% by mass, the hue variation of the image becomes large.
The lower limit of the content ratio of the carbon black pigment is preferably 65% by mass and more preferably 70% by mass from the viewpoint of further suppressing the hue variation of the image.
In the present invention, the upper limit of the content ratio of the carbon black pigment is not particularly limited, but from the viewpoint of more effectively obtaining the effects of the present invention, the upper limit is preferably 90% by mass, and 85 More preferably, it is more preferably 80% by mass.

In the present invention, the total amount of all pigments is 4% by mass or less with respect to the total amount of the black ink composition.
When the total amount of all the pigments exceeds 4% by mass, the hue variation becomes large, and the abrasion resistance and adhesion are deteriorated.
The lower limit of the total amount of all pigments is not particularly limited, but from the viewpoint of improving the optical density (OD) of the image, the lower limit is preferably 1.5% by mass, and is 1.8% by mass. More preferably, it is particularly preferably 2.0% by mass.

  Further, when the ink composition of the present invention contains both a magenta pigment and a cyan pigment, the mass ratio of the magenta pigment to the total mass of the magenta pigment and the cyan pigment [the mass of the magenta pigment / (the total mass of the magenta pigment and the cyan pigment) )] Is preferably 0.5 to 0.8, more preferably 0.5 to 0.7, from the viewpoint of hue.

<Resin>
In the present invention, the carbon black pigment and the at least one color pigment (hereinafter collectively referred to as “pigments”) are each coated with a resin at least partly from the viewpoint of dispersion stability. It is preferable that Hereinafter, a pigment having at least a part of its surface coated with a resin is also referred to as a “resin-coated pigment”.
Examples of the resin include polyvinyls, polyurethanes, and polyesters. Among them, polyvinyls are preferable.
The resin preferably has a salt-forming group from the viewpoint of dispersion stability.
Examples of the salt-forming group include an anionic group (hereinafter also referred to as “acidic group”) and a cationic group, and more specifically, a carboxy group, a sulfo group, a phosphonate group, an amino group, an ammonium group, and the like. Can be mentioned.
As the salt-forming group, an acidic group (for example, carboxy group, sulfonic acid group, phosphoric acid group) is preferable, and among them, a carboxyl group is particularly preferable.

The resin is preferably a water-soluble resin (hereinafter also referred to as “water-soluble resin”) from the viewpoint of dispersion stability.
Here, “water-soluble” means that the resin dissolves in 2% by mass or more in distilled water at 25 ° C., preferably 5% by mass or more, and more preferably 10% by mass or more. . In addition, when the resin has a salt-forming group (for example, an acidic group), it is preferable that the solubility is in the above range when neutralized with an equimolar amount of base or acid.
Examples of the water-soluble resin include hydrophilic polymer compounds. Among the hydrophilic polymer compounds, a water-soluble resin dispersant that disperses carbon black in an aqueous medium is preferable.

In the present invention, the resin having a salt-forming group that coats the pigment is preferably crosslinked with a crosslinking agent from the viewpoint of dispersion stability.
In this case, the resin preferably has a functional group that can be crosslinked by a crosslinking agent.
Examples of the crosslinkable functional group include the aforementioned salt-forming group (for example, carboxy group), isocyanate group, epoxy group and the like, and a carboxy group is particularly preferable from the viewpoint of improving dispersibility.
The pigment in the form of being coated with a resin having a salt-forming group and the resin being crosslinked with a crosslinking agent (hereinafter also referred to as “crosslinked resin-coated pigment”) is, for example, a resin having a salt-forming group. A resin-coated pigment can be prepared by dispersing the pigment, and then the resin of the resin-coated pigment can be prepared by crosslinking with a crosslinking agent.

Specifically, the resin-coated pigment is, for example,
(I) A step of mixing and dispersing a pigment, the water-soluble resin (dispersant), an aqueous solution containing a basic substance, and an organic solvent capable of dissolving or dispersing the water-soluble resin (mixing / hydration step) )When,
(Ii) a step of removing at least a part of the organic solvent (solvent removal step);
It can manufacture with the manufacturing method containing.
The cross-linked resin-coated pigment is, for example, between (i) and (ii) above,
(Iii) adding a crosslinking agent to the dispersion obtained by the dispersion treatment and heating to crosslink the water-soluble resin (crosslinking step);
(Iv) a step of purifying the dispersion after crosslinking to remove impurities (purification step);
It can manufacture with the manufacturing method containing.
By the above (i) to (iv), a pigment dispersion in which the pigment is finely dispersed and excellent in storage stability can be produced.
More specifically, for example, a pigment (resin-coated pigment) in which at least a part of the surface is coated with a water-soluble resin can be produced by the method described in JP-A-2009-190379.

The resin having a salt-forming group preferably has at least one of an aromatic ring structure and an alicyclic (hereinafter also referred to as “aliphatic ring”) structure from the viewpoint of dispersion stability.
In particular, in the ink composition, as long as the resin having a salt-forming group is not crosslinked, all of the resins covering the carbon black pigment and the at least one color pigment have an aromatic ring structure. From the viewpoint of dispersion stability.

  As a resin having at least one of an aromatic ring structure and an alicyclic structure and having a salt-forming group, specifically, a repeating unit represented by the following general formula (a) and a repeating unit having a salt-forming group And a resin (hereinafter also referred to as “specific resin”).

(Repeating unit represented by general formula (a))

In the general formula (a), R ₁ represents a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), and L ₁ represents ^* —COO—, ^* —OCO—, ^* —CONR ₂ —, ^* —O—, or a substituted or unsubstituted phenylene group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Incidentally, symbol * in the group represented by L ₁ represents a connecting point with the main chain. L ₂ represents a single bond or a divalent linking group. A ₁ represents a monovalent group derived from an aromatic ring or an aliphatic ring.

In the general formula (a), R ₁ represents a hydrogen atom, a methyl group, or a halogen atom, preferably a methyl group.

In the general formula (a), L ₁ represents ^* —COO—, ^* —OCO—, ^* —CONR ₂ —, ^* —O—, or a substituted or unsubstituted phenylene group. When L ₁ represents a phenylene group, unsubstituted is preferred. The L ₁ is particularly preferably ^* -COO-.
In the general formula (a), R ₂ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

L ₂ represents a single bond or a divalent linking group. The divalent linking group is preferably a linking group having 1 to 30 carbon atoms, more preferably a linking group having 1 to 25 carbon atoms, still more preferably a linking group having 1 to 20 carbon atoms, Particularly preferred is a linking group having 1 to 15 carbon atoms.
Among these, L ₂ is particularly preferably a single bond, an alkyleneoxy group having 1 to 20 carbon atoms (more preferably 1 to 10), an imino group (—NH—), a sulfamoyl group, and 1 to 20 carbon atoms (more Preferably a divalent linking group containing an alkylene group, such as an alkylene group of 1 to 15) or an ethylene oxide group [— (CH ₂ CH ₂ O) _n —, where n is an integer of 1 to 6], and the like. Groups that combine more than one species.
Among them, L ₂ is most preferably a single bond, an alkylene group having 1 to 20 carbon atoms (more preferably 1 to 15, more preferably 1 to 6), an ethylene oxide group [— (CH ₂ CH ₂ O) _n — ^{*. *;} n = 1 to 6 integer, ** is] represents a bonding position to _{a 1.}

In the general formula (a), A ₁ represents a monovalent group derived from an aromatic ring or an aliphatic ring.
When A ₁ is a monovalent group derived from an aromatic ring, the aromatic ring is not particularly limited, but a benzene ring, a condensed aromatic ring having 8 or more carbon atoms, an aromatic ring condensed with a hetero ring An aromatic ring in which two or more benzene rings are condensed is mentioned.
In addition, when A ₁ is a monovalent group derived from an aliphatic ring, the aliphatic ring is not particularly limited, but an aliphatic ring having 3 to 12 carbon atoms (preferably, a cyclohexane ring or an isobornene ring). Is mentioned.

  The “condensed aromatic ring having 8 or more carbon atoms” is an aromatic ring in which at least two benzene rings are condensed, or an alicyclic hydrocarbon condensed with at least one aromatic ring and the aromatic ring. And an aromatic compound having 8 or more carbon atoms in which a ring is formed. Specific examples include naphthalene, anthracene, fluorene, phenanthrene, acenaphthene and the like.

The “aromatic ring condensed with a heterocycle” is a compound in which an aromatic compound containing no hetero atom (preferably a benzene ring) and a cyclic compound having a hetero atom are condensed. Here, the cyclic compound having a hetero atom is preferably a 5-membered ring or a 6-membered ring. As a hetero atom, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable. The cyclic compound having a hetero atom may have a plurality of hetero atoms. In this case, the heteroatoms may be the same or different from each other.
Specific examples of the heterocyclic ring condensed with an aromatic ring include phthalimide, acridone, carbazole, benzoxazole, and benzothiazole.

  Specific examples of the monomer forming the repeating unit represented by the general formula (a) include vinyl monomers such as (meth) acrylates, (meth) acrylamides, styrenes, and vinyl esters. it can.

  In the specific resin, the repeating unit represented by the general formula (a) has a structure in which an aromatic ring or an aliphatic ring is bonded to an atom forming a main chain through a linking group, that is, an aromatic ring or an aliphatic ring. Has a structure that does not directly bond to the atoms forming the main chain. For this reason, since an appropriate distance is maintained between the hydrophobic aromatic ring or aliphatic ring and the repeating unit having a salt-forming group, an interaction is likely to occur between the specific resin and the pigment. Therefore, the specific resin is more strongly adsorbed to the pigment, thereby further improving the dispersibility of the pigment.

Specific examples of the monomer that forms the repeating unit represented by the general formula (a) include the following monomers as monomers having an aromatic ring.
However, the present invention is not limited to these.

  Specific examples of the monomer that forms the repeating unit represented by the general formula (a) include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate as the monomer having an aliphatic ring. However, the present invention is not limited to these.

  As a monomer that forms the repeating unit represented by the general formula (a), from the viewpoint of dispersion stability of the coated pigment, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, Isobornyl (meth) acrylate is preferred.

The repeating unit represented by the general formula (a) can be used alone or in combination of two or more.
The content of the repeating unit represented by the general formula (a) in the polymer is preferably in the range of 20 to 90% by mass, more preferably 45 to 90% by mass with respect to the total mass of the polymer. Especially preferably, it is the range of 65-90 mass%.

(Repeating unit having a salt-forming group)
The repeating unit having a salt-forming group is preferably a repeating unit derived from a salt-forming group-containing monomer.
Examples of the salt-forming group-containing monomer include a cationic monomer and an anionic monomer. Examples thereof include those described in JP-A-9-286939, page 5, column 7, line 24 to column 8, line 29.

  Representative examples of the cationic monomer include unsaturated amino group-containing monomers and unsaturated ammonium salt-containing monomers. Among these, N, N-dimethylaminoethyl (meth) acrylate and N- (N ′, N′-dimethylaminopropyl) (meth) acrylamide are preferable.

Representative examples of anionic monomers include unsaturated carboxylic acid monomers, unsaturated sulfonic acid monomers, unsaturated phosphoric acid monomers, and the like.
Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, β-carboxyethyl acrylate, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid.
Examples of unsaturated sulfonic acid monomers include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, and bis- (3-sulfopropyl) -itaconate.
Examples of unsaturated phosphoric acid monomers include vinylphosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxy Examples thereof include ethyl phosphate.
As the salt-forming group-containing monomer, the anionic monomer is preferable. Among them, an unsaturated carboxylic acid monomer is more preferable, and acrylic acid or methacrylic acid is particularly preferable from the viewpoints of dispersion stability, dischargeability, and the like.

The specific resin may contain other repeating units.
Examples of other repeating units include repeating units derived from alkyl (meth) acrylates having 1 to 20 carbon atoms; styrene and derivatives thereof;

  The method for synthesizing the specific polymer is not particularly limited, but random polymerization of vinyl monomers is preferable from the viewpoint of dispersion stability.

The resin having a salt-forming group includes at least one of an alkyl (meth) acrylate having 1 to 20 carbon atoms, a (meth) acrylate having an aromatic ring group, and a (meth) acrylate having an alicyclic group, and a carboxyl group-containing resin. And a copolymer obtained using the monomer.
Among them, as the resin having the salt-forming group, at least one of benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate, (meth) acrylic acid, , A repeating unit derived from at least one of benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. , A copolymer containing at least a repeating unit derived from (meth) acrylic acid).

From the viewpoint of pigment dispersibility, the resin preferably has an acid value (acid value before crosslinking when the resin is crosslinked) of 50 to 250 mgKOH / g, preferably 50 to 150 mgKOH / g. It is more preferable. The acid value of the resin is measured by the method described in JIS standard (JIS K0070: 1992).
When the resin is crosslinked, the crosslinking rate of the resin is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, more preferably from the viewpoint of dispersion stability of the pigment and cohesiveness of the ink. Preferably it is 10-45 mol%. Here, the crosslinking rate (mol%) refers to a value determined by the following formula.
Crosslink rate (mol%) = [number of mole equivalents of crosslinking agent to be reacted with 1 mole of polymer × 100 / number of moles of reactive group capable of reacting with crosslinking agent of 1 mole of polymer]
Here, “the number of molar equivalents of the crosslinking agent to be reacted with 1 mol of the polymer” is a value obtained by multiplying the number of moles of the crosslinking agent to be reacted with 1 mol of the polymer by the number of reactive groups in one molecule of the crosslinking agent.

From the viewpoint of pigment dispersibility, the resin preferably has a weight average molecular weight (when the resin is crosslinked, the weight average molecular weight before crosslinking) of 3,000 to 100,000, preferably 5,000 to 80,000. 000 is more preferable, and 10,000 to 60,000 is still more preferable.
The weight average molecular weight of the resin was determined by using a GPC analyzer equipped with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation), using THF as a solvent, and differential refraction. The molecular weight is detected by a meter and expressed in terms of polystyrene as a standard substance.

  The mass ratio [resin mass / pigment mass] of the resin and the pigment in the black ink composition is preferably 0.30 to 0.80 from the viewpoint of ink stability.

In the present invention, when a water-soluble resin is used as the resin, in addition to the water-soluble resin, a water-insoluble resin (for example, a water-insoluble dispersant) may be used in combination.
As the water-insoluble resin, a water-insoluble resin having a hydrophobic structural unit and a hydrophilic structural unit can be used. The hydrophilic structural unit is preferably a structural unit having a salt-forming group, more preferably a structural unit having an acidic group, and particularly preferably a structural unit having a carboxy group.
Examples of the water-insoluble resin include styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid. Examples include copolymers, polyethylene glycol (meth) acrylate- (meth) acrylic acid copolymers, vinyl acetate-maleic acid copolymers, and styrene-maleic acid copolymers.
More specifically, for example, the water-insoluble resins described in JP-A-2005-41994, JP-A-2006-238991, JP-A-2009-084494, JP-A-2009-191134, and the like are preferably used in the present invention. Can be used.

(Crosslinking agent)
The resin covering the pigment in the resin-coated pigment is preferably crosslinked with a crosslinking agent.
The cross-linking agent is not particularly limited as long as it is a compound having two or more sites that react with the resin, but preferably has two or more epoxies from the viewpoint of excellent reactivity with a carboxy group. It is a compound (a bifunctional or higher functional epoxy compound) having a group.
Specific examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylol propane tri Examples thereof include glycidyl ether, and polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether are preferable.

  A commercial item can also be used as said crosslinking agent. As a commercial item, Dencol EX-321, EX-821, EX-830, EX-850, EX-851 (made by Nagase ChemteX Corporation) etc. can be used, for example.

  The molar ratio of the crosslinking site (for example, epoxy group) of the crosslinking agent to the crosslinked site (for example, carboxy group) of the resin is 1: 1 to 1:10 from the viewpoint of the crosslinking reaction rate and the dispersion stability after crosslinking. Is preferable, 1: 1 to 1: 5 is more preferable, and 1: 1 to 1: 1.5 is most preferable.

<Water-soluble polymerizable compound>
The black ink composition of the present invention contains at least one water-soluble polymerizable compound.
Thereby, the black ink composition of the present invention is polymerized and cured by irradiation with active energy rays (for example, radiation, light, or electron beam).
Here, “water-soluble” means that it can be dissolved in water at a certain concentration or more. Specifically, the solubility in water at 25 ° C. is preferably 5% by mass or more, and more preferably 10% by mass or more. The water-soluble polymerizable compound is preferably one that can be dissolved (desirably uniformly) in the aqueous ink composition. Further, the solubility may be increased by adding a water-soluble organic solvent to be described later, and it may be dissolved (desirably uniformly) in the ink composition.

The water-soluble polymerizable compound in the present invention is not particularly limited, and may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound.
The water-soluble polymerizable compound preferably contains at least one selected from the group consisting of a compound having a (meth) acrylic ester structure in the molecule and a compound having a (meth) acrylamide structure in the molecule. More preferably, at least one compound having a (meth) acrylamide structure is contained therein. Here, the (meth) acrylic ester structure means at least one of a methacrylic ester structure and an acrylic ester structure, and the (meth) acrylamide structure means at least one of a methacrylamide structure and an acrylamide structure.

(Compound having (meth) acrylic ester structure in the molecule)
The polymerizable compound having a (meth) acrylic ester structure in the molecule is not limited as long as it is water-soluble and has a (meth) acrylic ester structure in the molecule, and is a monofunctional polymerizable compound. It may be a polyfunctional polymerizable compound.

  Examples of the monofunctional polymerizable compound having a (meth) acrylic ester structure in the molecule include hydroxyethyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate.

  The polyfunctional polymerizable compound having a (meth) acrylic ester structure in the molecule is preferably a compound represented by the following general formula (M-1).

In General Formula (M-1), Q ¹ represents an i-valent linking group, and R ¹ represents a hydrogen atom or a methyl group. I represents an integer of 2 or more.

Compound represented by the general formula (M-1) are those unsaturated monomer bonded to the linking group Q ¹ by an ester bond. R ¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. The valence i of the linking group Q ¹ is not limited, but is preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less.

The linking group Q ¹ is not particularly limited as long as it is a group that can be linked to the (meth) acrylic ester structure, but the compound represented by the general formula (M-1) can satisfy the aforementioned water solubility. It is preferable to select from such a linking group. Specific examples include residues from which one or more hydrogen atoms or hydroxyl groups have been removed from the following compound group X.

-Compound group X-
Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 -Butanediol, 2,3-butanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4 -Pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,5 -Pentanetriol, thioglycol, Methylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, neopentyl glycol, pentaerythritol, dipentaerythritol, and their condensates, low molecular weight polyvinyl alcohol, or polyols such as sugars, ethylenediamine, diethylenetriamine, triethylene Polyamines such as tetramine, polyethyleneimine, and polypropylenediamine.

Still linking group Q ^1, methylene, ethylene, propylene, 4 or less of the substituted or unsubstituted alkylene chain of carbon atoms such as butylene group, more pyridine ring, an imidazole ring, a pyrazine ring, piperidine ring, piperazine ring, morpholine ring Examples thereof include a functional group having a saturated or unsaturated heterocyclic ring.

Among these, the linking group Q ¹ is preferably a residue of a polyol containing an oxyalkylene group (preferably an oxyethylene group), and contains three or more oxyalkylene groups (preferably an oxyethylene group). A residue of a polyol is particularly preferable.

  Specific examples of the water-soluble polymerizable compound having a (meth) acrylic ester structure in the molecule include the following nonionic compounds, but the present application is not limited thereto.

  Further, as the nonionic polymerizable compound, a (meth) acrylic acid ester having two or more acryloyl groups in one molecule derived from a polyol compound can also be used. Examples of the polyol compound include polyol compounds having two or more hydroxyl groups such as glycol condensates, oligoethers, oligoesters, monosaccharides, and disaccharides.

  Also suitable are (meth) acrylic acid esters with triethanolamine, diethanolamine, trishydroxyaminomethane, trishydroxyaminoethane, and the like.

-Compounds with (meth) acrylamide structure in the molecule-
The compound having a (meth) acrylamide structure in the molecule is not particularly limited as long as it is a polymerizable compound having a (meth) acrylamide structure in the molecule, and even if it is a monofunctional polymerizable compound, it is a polyfunctional polymerizable compound. It may be a compound.

  Monofunctional polymerizable compounds having a (meth) acrylamide structure in the molecule include hydroxyethyl (meth) acrylamide, hydroxypropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide. Particularly preferred is hydroxyethyl (meth) acrylamide, and most preferred is hydroxyethylacrylamide.

  The polyfunctional polymerizable compound having a (meth) acrylamide structure in the molecule is preferably a compound represented by the following general formula (M-2). It is preferable to have the structure of the formula (M-2) because the compatibility between the compound represented by the general formula (1) described later and the polymerizable compound can be improved and the curing sensitivity can be increased.

In General Formula (M-2), Q ² represents a j-valent linking group, and R ² represents a hydrogen atom or a methyl group. J represents an integer of 2 or more.

The compound represented by formula (M-2) are those unsaturated monomers, bonded to the linking group Q ² by an amide bond. R ² represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Not limited to the valence j of the linking group Q ² but, more preferably 2 to 6 or less, still more preferably 2 to 4.

The connecting group Q ² is not particularly limited as long as it is capable of linking groups and (meth) acrylamide structure. Details of the linking group Q ² is the same as the linking group Q ^1, preferred embodiment is also the same.

  Specific examples of the water-soluble polymerizable compound having a (meth) acrylamide structure in the molecule include the following water-soluble polymerizable compounds.

  In addition to the polymerizable compound, for example, a compound having a maleimide structure typified below, a compound having a sulfamide structure, a compound having an N-vinylacetamide structure, or the like can also be used.

A water-soluble polymeric compound can be contained individually by 1 type or in combination of 2 or more types.
The total content of the polymerizable compound in the ink composition is preferably 3 to 50% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass with respect to the total mass of the ink composition.

In the ink composition of the present invention, when the water-soluble polymerizable compound contains both a monofunctional polymerizable compound and a polyfunctional polymerizable compound, the effect of improving adhesion is more effectively exhibited.
That is, generally, an ink composition using a monofunctional polymerizable compound tends to have insufficient curability and lower adhesion, but the ink composition of the present invention has a monofunctional polymerizable compound. Even when is used, the adhesion is easily maintained. For this reason, when the said water-soluble polymeric compound contains both a monofunctional polymeric compound and a polyfunctional polymeric compound, the effect of the adhesive improvement of this invention is show | played more notably.
When the water-soluble polymerizable compound contains a monofunctional polymerizable compound, the monofunctional polymerizable compound is a monofunctional polymerizable compound having a (meth) acrylamide structure from the viewpoint of further improving the adhesion. Is preferred.
Furthermore, when the water-soluble polymerizable compound contains a monofunctional polymerizable compound having a (meth) acrylamide structure, the abrasion resistance is improved.

  When the water-soluble polymerizable compound contains at least one monofunctional polymerizable compound having a (meth) acrylamide structure, the water-soluble polymerizable compound is a monofunctional polymerizable having the (meth) acrylamide structure. It is particularly preferable that at least one kind of a polyfunctional polymerizable compound (preferably a polyfunctional polymerizable compound having a (meth) acrylamide structure) is contained in addition to at least one kind of compound.

  When the water-soluble polymerizable compound includes a monofunctional polymerizable compound (for example, a monofunctional polymerizable compound having a (meth) acrylamide structure), the monofunctional polymerizable compound with respect to the total amount of the polymerizable compound contained in the ink composition. The content of the polymerizable compound (for example, a monofunctional polymerizable compound having a (meth) acrylamide structure) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 80% by mass, 40-80 mass% is especially preferable.

<Polymerization initiator>
The black ink composition of the present invention contains at least one polymerization initiator.
The polymerization initiator is preferably a water-soluble polymerization initiator. Here, the water solubility in the polymerization initiator means that 0.5% by mass or more dissolves in distilled water at 25 ° C. The water-soluble polymerization initiator is preferably dissolved at 1% by mass or more in distilled water at 25 ° C., more preferably at least 3% by mass.

  Examples of the water-soluble polymerization initiator include compounds represented by the following general formula (1), compounds described in JP-A-2005-307198, and the like. Especially, it is preferable that it is a water-soluble polymerization initiator represented by following General formula (1) from a viewpoint of adhesiveness and abrasion resistance.

In general formula (1), m and n each independently represent an integer of 0 or more, and m + n represents an integer of 0 to 3.
In the general formula (1), m is preferably 0 to 3 and n is preferably 0 or 1, more preferably m is 0 or 1 and n is 0.
Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (1) may be a compound synthesized according to the description in JP-A-2005-307198 or a commercially available compound. Examples of commercially available compounds represented by the general formula (1) include Irgacure 2959 (m = 0, n = 0).

  The content of the polymerization initiator in the ink composition of the present invention is preferably in the range of 0.1 to 30% by mass in terms of solid content, more preferably in the range of 0.5 to 20% by mass, The range is more preferably 1.0 to 15% by mass, and most preferably 1.0 to 5.0% by mass.

<Polymer containing repeating unit represented by general formula (i)>
The black ink composition of the present invention can contain a polymer containing a repeating unit represented by the following general formula (i) (hereinafter also simply referred to as “(component a)”). When the black ink composition of the present invention contains the (component a), the abrasion resistance of the image is further improved.
A plurality of repeating units represented by the general formula (i) present in the (component a) may be the same as or different from each other.

In general formula (i), m represents an integer of 2 to 15, and R ¹ represents a hydrogen atom or a methyl group.

In the general formula (i), R ¹ is preferably a hydrogen atom.
In the general formula (i), m is preferably an integer of 2 to 5, more preferably 3 or 5, and particularly preferably 3.
When a plurality of repeating units represented by the general formula (i) present in the (component a) are different from each other, the repeating unit in which the m in the general formula (i) is 3, and the m in the general formula (i) It is preferable that it contains the repeating unit which is 5.

  The (component a) preferably contains 50% by mass or more, more preferably 75-100% by mass of the repeating unit represented by the general formula (i) with respect to the total amount of the (component a), 80 It is particularly preferable to contain ~ 100% by mass.

  The (component a) preferably further contains a repeating unit represented by the following general formula (ii).

In the general formula (ii), R ² represents an alkyl group, and R ³ represents a hydrogen atom or a methyl group.

In the general formula (ii), the alkyl group represented by R ² is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, and a butyl group.
In the general formula (ii), the alkyl group represented by R ² is more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 carbon atom (that is, a methyl group).

In the formula (ii), R ³ is preferably a hydrogen atom.

  The (component a) preferably includes 1% by mass to 80% by mass of the repeating unit represented by the formula (ii) with respect to the total amount of the (component a), and includes 1% by mass to 50% by mass. It is more preferable to include 1% by mass to 10% by mass.

  The (component a) is preferably a molecular weight (weight average molecular weight for those having a molecular weight distribution) of 500 to 800,000, more preferably 800 to 100,000, and still more preferably 1,000 to 25,000.

  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. Is used.

  Specific examples of the (component a) include polyvinyl pyrrolidone (PVP K12 (manufactured by Acros), PVP K15, PVP K30 (all manufactured by ASP Japan)), vinyl pyrrolidone / vinyl acetate copolymer (Luvitec). VA64W, Luviskol VA37E (all manufactured by BASF Japan), PVP / VA W635 (manufactured by ASP Japan)), vinylpyrrolidone / vinylcaprolactam copolymer (Luvitec VPC K65W (manufactured by BASF Japan)), etc. Polyvinyl pyrrolidone (PVP K15, K30 (both manufactured by ISP Japan)), vinylpyrrolidone / vinyl acetate copolymer (PVP / VA W635 (manufactured by API Japan)), L viskol VA37E (manufactured by BASF · Japan Ltd.)), vinylpyrrolidone / vinylcaprolactam copolymer (Luvitec VPC K65W (manufactured by BASF · Japan)) is preferable.

When the black ink composition of the present invention contains the (component a), the (component a) may be contained singly or in combination of two or more.
When the black ink composition of the present invention contains the (component a), the content of the (component a) (the total content when there are two or more) is based on the total amount of the black ink composition. 0.1 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.5 to 5% by mass, and 0.5 to 3% by mass. It is particularly preferred.

<Colloidal silica>
The black ink composition of the present invention preferably further contains at least one kind of colloidal silica. By including the colloidal silica, the discharge stability is improved and a decrease in liquid repellency in the ink jet head member can be suppressed. The effect is particularly great when silicon is used in at least a part of the ink jet head member.
For example, the inclusion of colloidal silica effectively suppresses hydrolysis of the ink component and improves the stability of the ink composition, thereby stopping the ejection of the ink composition on the ink jet recording apparatus for a certain period of time. Even if it is allowed to stand and then discharge is restarted, it is considered that an excellent effect in discharge stability (stand-by recovery performance) can be obtained, and the rubbing resistance of the image can be compatible. Further, it is presumed that colloidal silica is appropriately adsorbed on the surface of the ink jet head member, and the surface erosion due to the ink component is alleviated, thereby preventing the liquid repellency from being lowered.

Colloidal silica is a colloid composed of fine particles of inorganic oxide containing silicon having an average particle size of several hundred nm or less. Silicon dioxide (including hydrates thereof) may be included as a main component, and aluminate may be included as a minor component. Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate.
In addition, colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic salts and organic salts act, for example, as colloid stabilizers.

  There is no restriction | limiting in particular as a dispersion medium of colloidal silica, Any of water, an organic solvent, and these mixtures may be sufficient. The organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent, but is preferably a water-soluble organic solvent. Specifically, methanol, ethanol, isopropyl alcohol, n-propanol etc. can be mentioned.

  There is no restriction | limiting in particular in the manufacturing method of colloidal silica, It can manufacture by the method used normally. For example, it can be produced from aerosil synthesis by thermal decomposition of silicon tetrachloride or water glass. Alternatively, it can also be produced by a liquid phase synthesis method such as hydrolysis of alkoxide (for example, see “Fiber and Industry”, Vol. 60, No. 7 (2004) P376).

Although there is no restriction | limiting in particular as an average particle diameter of the particle | grains contained in the colloidal silica in this invention, Preferably they are 1-25 nm, More preferably, they are 3-20 nm, More preferably, they are 3-15 nm, Especially preferably, 5 nm- 10 nm.
When the average particle size is 25 nm or less, damage (for example, decrease in liquid repellency) caused by ink to members constituting the inkjet head, such as a base material, a protective film, and a liquid repellent film, is more effectively suppressed. can do. This can be considered to be because, for example, the average particle diameter is small, the total surface area of the particles is increased, and damage to members constituting the inkjet head is more effectively suppressed. Furthermore, the average particle diameter of the particles is preferably 25 nm or less from the viewpoint of the dischargeability of the ink composition and the abrasive effect of the particles. In addition, when the average particle diameter is 1 nm or more, productivity is improved and colloidal silica with little variation in performance can be obtained.

In the present invention, the average particle diameter of colloidal silica can be measured by a method such as a light scattering method or a laser diffraction method, which is a general measurement of dispersed particles, but in the present invention, as a more direct method, TEM (transmission type) The particle diameter (area equivalent circle diameter) of 300 arbitrarily selected colloidal silica particles is measured by an electron microscope) imaging method, and is calculated as an arithmetic average thereof. That is, the average particle diameter of colloidal silica that can be used in the present invention represents the arithmetic average particle diameter of the equivalent area circle diameter.
The shape of the colloidal silica is not particularly limited as long as it does not hinder the ink ejection performance. For example, any of a spherical shape, a long shape, a needle shape, and a bead shape may be used. Among them, the spherical shape is preferable from the viewpoint of ink ejection.

<Surfactant>
The black ink composition of the present invention preferably contains at least one surfactant. The surfactant can be used as a surface tension adjusting agent.
As the surface tension modifier, a compound having a structure having both a hydrophilic part and a hydrophobic part in the molecule can be used effectively. Anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic properties Either a surfactant or a betaine surfactant can be used.
In the present invention, a nonionic surfactant is preferable from the viewpoint of suppressing droplet ejection interference of the ink composition, and among them, an acetylene glycol surfactant is more preferable.

  Examples of acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7. -Alkylene oxide adduct of diol etc. can be mentioned, It is preferable that it is at least 1 sort (s) chosen from this. Examples of commercially available products of these compounds include E series such as Olphine E1010 manufactured by Nissin Chemical Industry Co., Ltd.

In the case where the surfactant (surface tension adjusting agent) is contained in the black ink composition, the surfactant has a surface tension of 20 to 60 mN / in from the viewpoint of satisfactorily discharging the ink composition by an ink jet method. It is preferable to contain the quantity of the range which can be adjusted to m, More preferably, it is 20-45 mN / m from the point of surface tension, More preferably, it is 25-40 mN / m.
The specific amount of the surfactant in the black ink composition of the surfactant is not particularly limited except that the range of the surface tension is preferable, and is preferably 0.1% by mass or more, more preferably. It is 0.1-10 mass%, More preferably, it is 0.2-3 mass%.

<Water-soluble organic solvent>
The black ink composition of the present invention contains at least water, but may contain at least one water-soluble organic solvent in addition to water.
The water-soluble organic solvent can obtain an effect of preventing drying, wetting or promoting penetration. In order to prevent drying, the ink adheres to and drys at the ink discharge port of the ejection nozzle and is used as an anti-drying agent to prevent clogging. For drying prevention and wetting, the vapor pressure is lower than that of water. A water-soluble organic solvent is preferred. Further, for penetration promotion, it can be used as a penetration enhancer that enhances ink permeability to paper.

  Examples of water-soluble organic solvents include, for example, alkanediols (polyhydric alcohols) such as glycerin, ethylene glycol, and propylene glycol; sugar alcohols; those having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol Alkyl alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl Ether, diethylene glycol mono-iso-propyl ether, ethylene glycol -N-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monoethyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono T-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, Dipropylene glycol mono-iso-propyl ether, tripropylene glycol monomethyl ester Glycol ethers such as such as ether and the like. These can be used individually by 1 type or in combination of 2 or more types.

<Resin particles>
The black ink composition in the present invention can contain resin particles as necessary.
In addition, the resin particles fix the ink composition, that is, the image by aggregating or destabilizing the ink to increase the viscosity of the ink when it comes into contact with the treatment liquid described later or a region on the recording medium on which it is dried. It is preferable to have a function of Such resin particles are preferably dispersed in at least one of water and an organic solvent.

Resin particles include acrylic resins, vinyl acetate resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins, butadiene resins, styrene resins, crosslinked acrylic resins, crosslinked styrene resins, and benzoguanamine resins. A phenol resin, a silicone resin, an epoxy resin, a urethane resin, a paraffin resin, a fluorine resin, or a latex thereof can be used. Preferred examples include acrylic resins, acrylic-styrene resins, styrene resins, cross-linked acrylic resins, and cross-linked styrene resins.
The resin particles can also be used in the form of latex.

The weight average molecular weight of the resin particles is preferably 10,000 or more and 200,000 or less, more preferably 20,000 or more and 200,000 or less.
The volume average particle size of the resin particles is preferably in the range of 1 nm to 1 μm, more preferably in the range of 1 nm to 200 nm, still more preferably in the range of 1 nm to 100 nm, and particularly preferably in the range of 1 nm to 50 nm. In addition, the volume average particle diameter of the resin particles can be measured with a nanotrack particle size distribution measuring apparatus UPA-EX150 (manufactured by Nikkiso Co., Ltd.).
The glass transition temperature Tg of the resin particles is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.

It is preferable to use self-dispersing resin particles (self-dispersing resin particles) as the resin particles.
Here, the self-dispersing resin is a dispersion state in an aqueous medium due to a functional group (especially a salt-forming group) possessed by the polymer itself when it is dispersed by a phase inversion emulsification method in the absence of a surfactant. Refers to the water-insoluble polymer obtained. Specific examples of the salt-forming group that the self-dispersing resin may have are the same as the salt-forming group in the resin that coats the pigment, and the preferred range is also the same.
Here, the dispersed state refers to an emulsified state (emulsion) in which a water-insoluble polymer is dispersed in an aqueous medium and a dispersed state (suspension) in which a water-insoluble polymer is dispersed in an aqueous medium. It includes both states.
As the self-dispersing resin particles, the self-dispersing resin particles described in paragraphs 0090 to 0121 of JP2010-64480A and paragraphs 0130 to 0167 of JP2011-068805A can be used. .

The addition amount of the resin particles is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 5% by mass with respect to the black ink composition.
Moreover, there is no restriction | limiting in particular regarding the particle size distribution of a resin microparticle, What has a wide particle size distribution or a thing with a monodispersed particle size distribution may be sufficient. Two or more kinds of resin particles having a monodispersed particle size distribution may be mixed and used.

<Other ingredients>
The black ink composition may further contain various additives as other components, if necessary, in addition to the above components.
Examples of the various additives include, for example, ultraviolet absorbers, antifading agents, antifungal agents, pH adjusters, rust inhibitors, antioxidants, emulsion stabilizers, preservatives, antifoaming agents, viscosity modifiers, and dispersions. Known additives such as stabilizers or chelating agents can be used. The content of these additives may be appropriately determined according to the application, but may be, for example, about 0.02 to 1.00% by mass in the black ink composition.

<Physical properties of black ink composition>
The surface tension (25 ° C.) of the ink composition in the invention is preferably from 20 mN / m to 60 mN / m. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 40 mN / m or less.
The surface tension is measured under conditions of 25 ° C. using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

Further, the viscosity at 25 ° C. of the ink composition in the invention is preferably 1.2 mPa · s or more and 15.0 mPa · s or less, more preferably 2 mPa · s or more and less than 13 mPa · s, and further preferably. Is 2.5 mPa · s or more and less than 10 mPa · s.
The viscosity is measured using a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD) under conditions of 25 ° C.

<Manufacturing method>
The black ink composition can be produced by a conventional method. For example, a pigment dispersion containing at least one color pigment and a carbon black pigment (or each pigment dispersion prepared for each pigment type), at least one water-soluble polymerizable compound, and a polymerization initiator It can manufacture by mixing at least 1 sort (s), water, and other components (surfactant etc.) as needed. The mixing method is not particularly limited, and a commonly used mixing method can be appropriately selected and applied.

≪Ink set≫
The ink set of the present invention comprises at least one treatment liquid containing at least one kind of the black ink composition of the present invention described above and an aggregating agent capable of forming an aggregate by contact with the black ink composition. Seeds.
By using a treatment liquid in addition to the black ink composition and forming an image by an image forming method described later, an image having further excellent adhesion and abrasion resistance can be formed. In addition, an image having excellent film strength can be obtained.
Further, by using the treatment liquid, it is possible to increase the speed of ink jet recording, and even when recording at high speed, hue variation is suppressed and an image having excellent adhesion and abrasion resistance can be obtained. Even with high-speed recording, it is possible to obtain an image with high density and resolution and excellent drawing performance (for example, reproducibility of fine lines and fine portions).

<Processing liquid>
The treatment liquid contains at least one kind of aggregating agent capable of forming an aggregate by contact with the black ink composition described above, and further contains other components as necessary.

The flocculant in the present invention is capable of aggregating (fixing) components in the ink composition by contacting the ink composition on the recording medium, and functions as, for example, a fixing agent. For example, when the treatment liquid is applied to a recording medium (preferably coated paper), the ink composition further drops and comes into contact with the aggregating agent while the aggregating agent is present on the recording medium. The components in the ink composition can be agglomerated to fix the ink composition component on the recording medium.
Examples of the flocculant include acidic compounds, polyvalent metal salts, and cationic polymers. Among these, an acidic compound is preferable from the viewpoint of cohesiveness of the ink composition component. A flocculant may be used individually by 1 type, or may use 2 or more types together.

-Acidic compounds-
Examples of acidic compounds include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, and tartaric acid. , Lactic acid, sulfonic acid, orthophosphoric acid, metaphosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, and derivatives of these compounds, etc. Preferably mentioned.

Among these, acidic compounds with high water solubility are preferable. Further, from the viewpoint of fixing the whole ink by reacting with the ink composition component, a trivalent or lower valent acidic compound is preferable, and a divalent or trivalent acidic compound is particularly preferable.
An acidic compound may be used individually by 1 type, and may use 2 or more types together.

  When the treatment liquid contains an acidic compound, the pH (25 ° C.) of the treatment liquid is preferably 0.1 to 6.8, more preferably 0.5 to 6.0, 0.8 More preferably, it is -5.0.

  The content of the acidic compound is preferably 40% by mass or less, more preferably 15 to 40% by mass, and 15 to 35% by mass with respect to the total mass of the treatment liquid. Further preferred. By setting the content of the acidic compound to 40% by mass or less, the components in the ink composition can be more efficiently fixed.

-Multivalent metal salt-
Examples of the polyvalent metal salt include alkaline earth metals belonging to Group 2 of the periodic table (eg, magnesium, calcium), transition metals belonging to Group 3 of the periodic table (eg, lanthanum), and Group 13 of the periodic table. Cation (for example, aluminum) and the salt of lanthanides (for example, neodymium) can be mentioned. As these metal salts, carboxylate (formic acid, acetic acid, benzoate, etc.), nitrate, chloride, and thiocyanate are suitable. Among them, preferred are calcium salts or magnesium salts of carboxylic acids (formic acid, acetic acid, benzoates, etc.), calcium salts or magnesium salts of nitric acid, calcium chloride, magnesium chloride, and calcium salts or magnesium salts of thiocyanic acid.
The said polyvalent metal salt can be used individually by 1 type or in mixture of 2 or more types.

It is preferable that content of the said polyvalent metal salt is 15 mass% or more with respect to the total mass of the said process liquid. By setting the content of the polyvalent metal salt to 15% by mass or more, the components in the ink composition can be more effectively fixed.
The content of the polyvalent metal salt is preferably 15% by mass to 35% by mass with respect to the total mass of the treatment liquid.

-Cationic polymer-
The cationic polymer is at least one cationic polymer selected from poly (vinyl pyridine) salt, polyalkylaminoethyl acrylate, polyalkylaminoethyl methacrylate, poly (vinyl imidazole), polyethyleneimine, polybiguanide, and polyguanide. is there.
A cationic polymer may be used individually by 1 type, and may use 2 or more types together.
Among the cationic polymers, polyguanides (preferably poly (hexamethyleneguanidine) acetate, polymonoguanide, polymeric biguanide), polyethyleneimine, and poly (vinylpyridine), which are advantageous from the viewpoint of aggregation rate, are preferable.

  The weight average molecular weight of the cationic polymer is preferably smaller in terms of the viscosity of the treatment liquid. When the treatment liquid is applied to the recording medium by an inkjet method, a range of 500 to 500,000 is preferable, a range of 700 to 200,000 is more preferable, and a range of 1,000 to 100,000 is more preferable. . When the weight average molecular weight is 500 or more, it is advantageous from the viewpoint of aggregation speed, and when it is 500,000 or less, it is advantageous from the viewpoint of ejection reliability. However, this is not the case when the treatment liquid is applied to the recording medium by a method other than inkjet.

  When the treatment liquid contains a cationic polymer, the pH (25 ° C.) of the treatment liquid is preferably 1.0 to 10.0, more preferably 2.0 to 9.0, and 3. More preferably, it is 0-7.0.

  The content of the cationic polymer is preferably 1% by mass to 35% by mass and more preferably 5% by mass to 25% by mass with respect to the total mass of the treatment liquid.

  The treatment liquid preferably contains at least one water-soluble organic solvent in addition to the flocculant. The details of the water-soluble organic solvent are the same as those in the ink composition, and the preferred embodiments are also the same.

  The treatment liquid can further contain other additives as other components within a range not impairing the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, anti-foaming agents. Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned.

≪Image formation method≫
In the image forming method of the present invention, the ink set of the present invention described above is used, and a treatment liquid application step of applying the treatment liquid to a recording medium, and an ink application step of applying the black ink composition to the recording medium. And a curing step of irradiating the image formed by the treatment liquid applying step and the ink applying step with an active energy ray to cure the image. The image forming method of the present invention may have other configurations as necessary.

  In the image forming method of the present invention, the components of the ink composition are aggregated with the aggregating agent contained in the processing liquid, and the active energy rays are irradiated onto this to polymerize and cure the polymerizable compound. An image having further excellent abrasion resistance can be formed. Further, the film strength of the image obtained by curing is further improved.

(Ink application process)
In the ink application process, the black ink composition of the present invention described above is applied onto the recording medium by, for example, an ink jet method. In this step, the ink composition can be selectively applied onto the recording medium, and a desired image can be formed.

  The inkjet method is not particularly limited, and is a known method, for example, a charge control method that discharges ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an electric method An acoustic ink jet system that converts a signal into an acoustic beam, irradiates the ink with ink and ejects the ink using radiation pressure, and a thermal ink jet (bubble jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. )) Any method may be used. The ink jet method includes a method of ejecting many low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method using is included.

In addition, an ink jet head used in the ink jet method may be an on-demand method or a continuous method. In addition, as a discharge method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion method (for example, a thermal type) Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.) and a discharge type (for example, a spark jet type). However, any discharge method may be used.
There are no particular restrictions on the ink nozzles used when recording by the ink jet method, and they can be appropriately selected according to the purpose.

  As an ink jet method, a short-type serial head is used, and a shuttle system that performs recording while scanning the head in the width direction of the recording medium, and a line head in which recording elements are arranged corresponding to the entire area of one side of the recording medium There is a line system using. In the line method, an image can be recorded on the entire surface of the recording medium by scanning the recording medium in a direction orthogonal to the arrangement direction of the recording elements, and a carriage system such as a carriage for scanning a short head is not necessary. Further, since complicated scanning control of the carriage movement and the recording medium is not required, and only the recording medium is moved, the recording speed can be increased as compared with the shuttle system. The ink jet recording method of the present invention can be applied to any of these, but generally, when applied to a line system in which no dummy jet is performed, the effect of improving ejection accuracy and image scratch resistance is great.

  The amount of ink droplets ejected from the inkjet head is preferably 0.5 to 6 pl (picoliter), more preferably 1 to 5 pl, and still more preferably 2 to 4 pl from the viewpoint of obtaining a high-definition image. .

(Processing liquid application process)
In the treatment liquid application step, the treatment liquid is applied to a recording medium, and the treatment liquid is brought into contact with the ink composition to form an image. In this case, dispersed particles such as resin particles and pigment in the ink composition are aggregated, and the image is fixed on the recording medium. The details and preferred embodiments of each component in the treatment liquid are as described above.

  The treatment liquid can be applied by applying a known method such as a coating method, an ink jet method, or an immersion method. As the coating method, a known coating method using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, or the like can be used. The details of the inkjet method are as described above.

The treatment liquid application step may be provided either before or after the ink application step using the ink composition.
In the present invention, it is preferable to provide an ink application step after applying the treatment liquid in the treatment liquid application step. That is, before applying (discharging) the ink composition to the recording medium by the ink jet method, a processing liquid capable of aggregating the pigment in the ink composition is applied in advance, and the processing liquid applied on the recording medium is applied. An embodiment in which an image is formed by discharging the ink composition so as to come into contact with the ink is preferable. Thereby, inkjet recording can be speeded up, and an image with high density and resolution can be obtained even at high speed recording.

The application amount of the treatment liquid is not particularly limited as long as the ink composition can be aggregated. However, the application amount is preferably such that the application amount of the flocculant is 0.1 g / m ² or more. Especially, the quantity from which the provision amount of a flocculant will be 0.1-1.0 g / m < ² > is preferable, More preferably, it is 0.2-0.8 g / m < ² >. When the amount of the aggregating component is 0.1 g / m ² or more, the agglomeration reaction proceeds favorably, and when it is 1.0 g / m ² or less, the glossiness is not excessively increased.

  In the present invention, an ink application step is provided after the treatment liquid application step, and the treatment liquid on the recording medium is heated and dried after the treatment liquid is applied on the recording medium and before the ink composition is applied. It is preferable to further provide a heat drying step. By heating and drying the treatment liquid in advance before the ink application step, ink colorability such as bleeding prevention is improved, and a visible image with good color density and hue can be recorded.

  Heating and drying can be performed by a known heating means such as a heater, an air blowing means such as a dryer, or a combination of these. As the heating method, for example, a method of applying heat with a heater or the like from the side opposite to the treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the treatment liquid application surface of the recording medium, or an infrared heater was used. The heating method etc. are mentioned, You may heat combining these two or more.

(Heat drying process)
The image forming method of the present invention includes a heating and drying step of heating at least a part of the solvent in the ink composition by heating the ink image formed by applying the ink composition after the ink ejection step. Is preferred. By performing the heat drying treatment, an image having better adhesion and abrasion resistance can be formed by a subsequent curing step.

  The method of heating is not particularly limited, but a non-contact drying method such as a method of heating with a heating element such as a nichrome wire heater, a method of supplying warm air or hot air, a method of heating with a halogen lamp, an infrared lamp, etc. Preferably, it can be mentioned.

(Curing process)
The curing step is a step of irradiating the image formed by at least the treatment liquid applying step and the ink applying step with active energy rays to cure the image.
Examples of the active energy rays used here include α rays, γ rays, electron rays, X rays, ultraviolet rays, visible light, and infrared rays. Of these, ultraviolet rays are preferred.
By the curing step, the monomer component (water-soluble polymerizable compound) in the image can be surely polymerized and cured. At this time, if the light source for irradiating the active energy ray is disposed opposite to the recording surface of the recording medium and the entire recording surface is irradiated, the entire image can be cured. Note that an ultraviolet irradiation lamp, a halogen lamp, a high-pressure mercury lamp, a laser, an LED, an electron beam irradiation apparatus, or the like can be adopted as a light source for irradiating active energy rays.
The curing process for irradiating the active energy ray may be installed before or after the heat drying process, as long as it is after the ink application process and the treatment liquid application process. Also good.

The irradiation condition of the active energy ray is not particularly limited as long as the polymerizable compound can be polymerized and cured. For example, the wavelength of the active energy ray is, for example, preferably 200 to 600 nm, more preferably 300 to 450 nm, and further preferably 350 to 420 nm.
The output of the actinic energy ray is preferably at 5000 mJ / cm ² or less, more preferably 10~4000mJ / cm ^2, further preferably 20~3000mJ / cm ^2.

-Recording media-
The image forming method of the present invention records an image on a recording medium.
The recording medium is not particularly limited, and general printing paper mainly composed of cellulose, such as so-called high-quality paper, coated paper, and art paper, used for general offset printing and the like can be used. General printing paper mainly composed of cellulose is relatively slow in ink absorption and drying in image recording by a general ink jet method using water-based ink, and color material movement is likely to occur after droplet ejection, and image quality is likely to deteriorate. However, according to the image forming method using the ink set of the present invention, it is possible to record a high-quality image excellent in color density and hue by suppressing color material movement.

  As the recording medium, commercially available media can be used. For example, “OK Prince Quality” manufactured by Oji Paper Co., Ltd., “Shiraoi” manufactured by Nippon Paper Industries Co., Ltd., and Nippon Paper Industries Co., Ltd. Fine paper (A) such as “New NPI Fine” manufactured by Oji Paper Co., Ltd., “OK Everlight Coat” manufactured by Oji Paper Co., Ltd., and “Aurora S” manufactured by Nippon Paper Industries Co., Ltd., Oji Paper Co., Ltd. Lightweight coated paper (A3) such as “OK Coat L” manufactured by Nippon Paper Industries Co., Ltd. and “Aurora L” manufactured by Nippon Paper Industries Co., Ltd. “OK Top Coat +” manufactured by Oji Paper Co., Ltd. and Nippon Paper Industries Co., Ltd. Coated paper (A2, B2) such as “Aurora Coat” manufactured by Oji Paper Co., Ltd. Art paper (A1) such as “OK Kanto +” manufactured by Oji Paper Co., Ltd. and “Tokuhishi Art” manufactured by Mitsubishi Paper Industries Co., Ltd. Can be mentioned. It is also possible to use various photographic papers for ink jet recording.

Among these, from the viewpoint of obtaining a high-quality image having a large color material movement suppression effect and better color density and hue than before, the water absorption coefficient Ka is preferably 0.05 to 0.5. a recording medium mL ^/ m 2 ^{· ms 1/2,} more preferably recording medium 0.1~0.4mL ^/ m 2 ^{· ms 1/2,} more preferably 0.2-0.3 ml / It is a recording medium of m ² · ms ^1/2 .

  The water absorption coefficient Ka is synonymous with that described in JAPAN TAPPI paper pulp test method No. 51: 2000 (issued by Japan Paper Pulp Technology Association). Specifically, the absorption coefficient Ka is an automatic scanning absorption meter. It is calculated from the difference in the amount of water transferred between the contact time of 100 ms and the contact time of 900 ms using KM500Win (manufactured by Kumagai Riki Co., Ltd.).

  Among the recording media, so-called coated paper used for general offset printing is preferable. The coated paper is obtained by applying a coating material to the surface of high-quality paper, neutral paper, or the like that is mainly surface-treated with cellulose as a main component and is not surface-treated. The coated paper tends to cause quality problems such as image gloss and scratch resistance in image formation by ordinary aqueous inkjet, but in the inkjet recording method of the present invention, gloss unevenness is suppressed and gloss and resistance are reduced. An image having good rubbing properties can be obtained. In particular, it is preferable to use a coated paper having a base paper and a coat layer containing kaolin and / or calcium bicarbonate. More specifically, art paper, coated paper, lightweight coated paper, or finely coated paper is more preferable.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

<< Synthesis of Resin Dispersant P-1 >>
Synthesized according to the following.
A monomer feed composition was prepared by mixing methacrylic acid (172 parts), benzyl methacrylate (828 parts), and isopropanol (375 parts). An initiator feed composition was prepared by mixing 2,2-azobis (2-methylbutyronitrile) (22.05 parts) and isopropanol (187.5 parts).
Next, while isopropanol (187.5 parts) was heated to 80 ° C. in a nitrogen atmosphere, the mixture of the monomer supply composition and the initiator supply composition was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for further 4 hours, and then cooled to 25 ° C.
After cooling, the solvent was removed under reduced pressure to obtain a resin dispersant P-1 having a weight average molecular weight of about 50,000.

<< Preparation of Black Ink Composition (K1) >>
<Preparation of Black Pigment Dispersion K1>
The resin dispersant P-1 (150 parts) obtained above was neutralized with 0.8 potassium equivalent of the amount of methacrylic acid in the resin dispersant using an aqueous potassium hydroxide solution, and further ion-exchanged water was added. An aqueous resin dispersant solution was prepared so that the concentration of the resin dispersant was 20% by mass.
This aqueous resin dispersant solution (117 parts), carbon black pigment (# 95, manufactured by Mitsubishi Chemical Corporation) (52.5 parts), ion-exchanged water (75.5 parts), dipropylene glycol (105 parts) And a bead mill (bead diameter 0.1 mmφ, zirconia beads) until a desired volume average particle diameter is obtained, and dispersion N1 (uncrosslinked dispersion) of resin-coated black pigment particles having a pigment concentration of 15% by mass Product).
To the dispersion N1 (136 parts), ion exchange water (100 parts), Denacol EX-321 (0.9 parts), boric acid aqueous solution (boric acid concentration 4 mass% aqueous solution, 9.9 parts) were added, After 6 hours and a half reaction at 50 ° C, the mixture was cooled to 25 ° C. Furthermore, ion-exchanged water was added to the obtained crosslinked dispersion using a stirring type ultra holder (manufactured by ADVANTEC) and an ultrafiltration filter (fractional molecular weight 50,000, Q0500076E ultra filter, manufactured by ADVANTEC). After ultrafiltration, the dispersion is purified so that the dipropylene glycol concentration in the dispersion is 1% by mass or less with respect to the total mass of the pigment, and then concentrated to a pigment concentration of 15% by mass to obtain a black pigment dispersion K1 was obtained.
In addition, 0.1 part of the obtained black pigment dispersion K1 and 19.9 parts of ion-exchanged water were mixed, and this was used to perform secondary treatment with a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.). The volume average particle diameter of the particles was measured and found to be 145 nm.

<Preparation of Cyan Pigment Dispersion C1>
The resin dispersant P-1 (150 parts) obtained above was neutralized with 0.8 potassium equivalent of the amount of methacrylic acid in the resin dispersant using an aqueous potassium hydroxide solution, and further ion-exchanged water was added. An aqueous resin dispersant solution was prepared so that the concentration of the resin dispersant was 20% by mass.
This aqueous resin dispersant solution (117 parts), cyan pigment (Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.) (52.5 parts), ion-exchanged water (75.5 parts), dipropylene glycol (105 parts) and a bead mill (bead diameter 0.1 mmφ, zirconia beads) and dispersed until a desired volume average particle diameter is obtained, and a dispersion N2 of resin-coated cyan pigment particles having a pigment concentration of 15% by mass ( An uncrosslinked dispersion) was obtained.
To the dispersion N2 (136 parts), ion exchange water (100 parts), Denacol EX-321 (0.9 parts), boric acid aqueous solution (boric acid concentration 4 mass% aqueous solution, 9.9 parts) were added, After 6 hours and a half reaction at 50 ° C, the mixture was cooled to 25 ° C. Furthermore, ion-exchanged water was added to the obtained crosslinked dispersion using a stirring type ultra holder (manufactured by ADVANTEC) and an ultrafiltration filter (fractional molecular weight 50,000, Q0500076E ultra filter, manufactured by ADVANTEC). After ultrafiltration, the dispersion is purified so that the dipropylene glycol concentration in the dispersion is 1% by mass or less with respect to the total mass of the pigment, and then concentrated to a pigment concentration of 15% by mass to obtain a cyan pigment dispersion. C1 was obtained.
Further, 0.1 part of the obtained cyan pigment dispersion C1 and 19.9 parts of ion-exchanged water were mixed, and this was used to obtain a secondary by a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso Co., Ltd.). The volume average particle diameter of the particles was measured and found to be 80 nm.

<Preparation of Magenta Pigment Dispersion M1>
The resin dispersant P-1 (150 parts) obtained above was neutralized with 0.8 potassium equivalent of the amount of methacrylic acid in the resin dispersant using an aqueous potassium hydroxide solution, and further ion-exchanged water was added. An aqueous resin dispersant solution was prepared so that the concentration of the resin dispersant was 20% by mass.
This aqueous resin dispersant solution (78.8 parts), magenta pigment (Pigment Red 122, manufactured by Dainichi Seika Co., Ltd.) (52.5 parts), ion-exchanged water (106.7 parts), dipropylene glycol (112 parts) and a bead mill (bead diameter 0.1 mmφ, zirconia beads) and dispersed until a desired volume average particle diameter is obtained, and a dispersion N3 of resin-coated magenta pigment particles having a pigment concentration of 15% by mass ( An uncrosslinked dispersion) was obtained.
To the above dispersion N3 (136 parts), ion-exchanged water (100 parts), Denacol EX-321 (0.6 parts), boric acid aqueous solution (boric acid concentration 4 mass% aqueous solution, 6.6 parts) were added. After 6 hours and a half reaction at 50 ° C, the mixture was cooled to 25 ° C. Furthermore, ion-exchanged water was added to the obtained crosslinked dispersion using a stirring type ultra holder (manufactured by ADVANTEC) and an ultrafiltration filter (fractional molecular weight 50,000, Q0500076E ultra filter, manufactured by ADVANTEC). And then purifying the mixture so that the dipropylene glycol concentration in the dispersion is 1% by mass or less with respect to the total mass of the pigment, and then concentrating to a pigment concentration of 15% by mass to obtain a magenta pigment dispersion. M1 was obtained.
In addition, 0.1 part of the obtained magenta pigment dispersion M1 and 19.9 parts of ion-exchanged water were mixed, and this was used to obtain a secondary by Nanotrac particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.). The volume average particle diameter of the particles was measured and found to be 80 nm.

<Synthesis of Polymerizable Compound 2>
To a 1 L three-necked flask equipped with a stirrer was added 4,7,10-trioxa-1,13-tridecanediamine 40.0 g (182 mmol), sodium bicarbonate 37.8 g (450 mmol), water 100 g, and tetrahydrofuran 300 g. In an ice bath, 35.2 g (389 mmol) of acrylic acid chloride was added dropwise over 20 minutes. After dropping, the mixture was stirred at room temperature for 5 hours, and then tetrahydrofuran was distilled off from the obtained reaction mixture under reduced pressure. Next, the aqueous layer was extracted four times with 200 ml of ethyl acetate, and the obtained organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain 35.0 g of the target polymerizable compound 2 solid. (107 mmol, 59% yield).
The structure of the polymerizable compound 2 is shown below.

<Preparation of Black Ink Composition (Ink 1)>
The following composition was mixed and filtered through a glass filter (GS-25) manufactured by ADVANTEC, and then filtered through a filter (PVDF membrane, pore size 5 μm) manufactured by Millipore to prepare a black ink composition (ink 1).

-Composition of black ink composition (ink 1)-
Black pigment dispersion K1 14.7 parts Cyan pigment dispersion C1 2 parts Magenta pigment dispersion M1 3.3 parts Polymeric compound 2 10 parts Hydroxyethyl acrylamide 10 parts Olfine E1010 (Nissin Chemical Industry Co., Ltd., surfactant) ... 1 part · Polyvinylpyrrolidone (PVP K15, made by IS Japan) · 1 part · Irgacure 2959 (BASF Japan Ltd .; photopolymerization initiator) ) ... 3 parts, ion-exchanged water ... Remaining amount of 100 parts in total

<Preparation of Black Ink Composition (Inks 2, 3, 6, 7, 13, 14)>
In the production of the black ink composition (ink 1), the carbon black pigment, cyan pigment, and magenta pigment contents were changed as shown in Table 1 below, and if necessary, ion-exchanged water in the ink composition. A black ink composition (inks 2, 3, 6, 7, 13, 14) was prepared in the same manner as the black ink composition (ink 1) except that the amount was adjusted to 100 parts for the entire ink. .

<Preparation of Black Ink Composition (Inks 9 to 12)>
In the production of the black ink composition (ink 1), the total amount of hydroxyethyl acrylamide and the polymerizable compound 2 in the black ink composition was fixed to 20 parts, and then the total amount of hydroxyethyl acrylamide and the polymerizable compound 2 ( That is, the black ink composition (ink 1) except that the ratio (mass%) of hydroxyethylacrylamide (that is, monofunctional polymerizable compound) to the total amount of polymerizable compound was changed as shown in Table 1 below. In the same manner as described above, black ink compositions (inks 9 to 12) were prepared.

<Preparation of Black Ink Composition (Inks 4, 5, 8, 15)>
In preparation of black ink composition (ink 1) (specifically, preparation of black dispersion K1), the type and content of carbon black pigment and the content of magenta pigment were changed as shown in Table 1 below. Produced black ink compositions (inks 4, 5, 8, 15) in the same manner as the black ink composition (ink 1).
In Table 1, Printex35 and Printex200 are both carbon black pigments manufactured by Evonik Degussa, and MA11 and MA14 are both carbon black pigments manufactured by Mitsubishi Chemical Corporation.

≪Preparation of treatment liquid≫
The processing liquid was prepared by mixing components having the following composition.
The viscosity, surface tension, and pH (25 ± 1 ° C.) of the treatment liquid were a viscosity of 2.5 mPa · s, a surface tension of 40 mN / m, and a pH of 1.0.
Here, the surface tension was measured using a fully automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd., and the viscosity was measured using DV-III Ultra CP manufactured by Brookfield Engineering. The pH was measured using a PH meter HM-30R manufactured by Toa DKK Co., Ltd.

~ Composition of treatment liquid ~
・ Malonic acid (Wako Pure Chemical Industries, Ltd.) ... 11.3%
・ DL-malic acid (manufactured by Fuso Chemical Industry Co., Ltd.) 14.5%
・ Tripropylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.0%
・ Diethylene glycol monobutyl ether (Daicel Chemical Industries, Ltd .... 4.0%
・ Ion-exchanged water ... Total remaining amount of 100%

<< Image formation and evaluation >>
<Image formation>
A printer for evaluation equipped with a GELJET GX5000 printer head (full line head manufactured by Ricoh) was prepared, and the black ink composition obtained above was refilled in a storage tank connected to the printer. “Special Rhibo Art Double Side N” manufactured by Mitsubishi Paper Industries Co., Ltd. as a recording medium was fixed on a stage movable in a predetermined linear direction at 500 mm / second, and the stage temperature was maintained at 30 ° C. The treatment liquid obtained above was applied to this in an amount of about 1.5 g / m ² with a wire bar coater, and dried at 50 ° C. for 2 seconds immediately after the application.
Thereafter, the inkjet head is fixedly arranged so that the direction of the line head in which the nozzles are arranged (main scanning direction) is inclined by 75.7 degrees with respect to the direction orthogonal to the moving direction of the stage (sub-scanning direction), and recording is performed. While moving the medium at a constant speed in the sub-scanning direction, a solid image was recorded by ejecting ink by a line system under ejection conditions of an ink droplet amount of 3 pL, an ejection frequency of 25.5 kHz, and a resolution of 1200 dpi × 1200 dpi. After the image was recorded, while being heated from the back side (back side) of the ink landing surface with an infrared heater, the recording surface was dried by applying warm air of 120 ° C. and 5 m / sec for 15 seconds. After the image was dried, UV light (a metal halide lamp manufactured by Eye Graphics Co., Ltd., maximum irradiation wavelength 365 nm) was irradiated so as to obtain an integrated irradiation amount of 0.8 J / cm ² to cure the image to obtain a print sample.

<Rubbing resistance evaluation>
The print sample obtained above was left in an environment of 25 ° C. and 50% RH for 15 minutes. On the surface of the solid image of the sample after being allowed to stand, the double-sided Nishi-Nishi Art N (hereinafter referred to as an unused sample in this evaluation) was superimposed and rubbed 10 times with a load of 200 kg / m ² . Thereafter, unused samples and solid images were visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

~ Evaluation criteria for abrasion resistance ~
A: Adherence of color to an unused sample was not recognized, and deterioration of the rubbed solid image was not observed.
B: Slight adhesion of color to the unused sample was observed, but deterioration of the rubbed solid image was not observed.
C: Adherence of color to an unused sample was recognized, and a part of the rubbed solid image (less than half of the solid image area) was deteriorated.
D: Adhesion of color to an unused sample was observed, and more than half of the rubbed solid image area was deteriorated.
* D is a level that is problematic in practice.

<Adhesion evaluation>
The print sample obtained above was left in an environment of 25 ° C. and 50% RH for 15 minutes. A 3 cm long cello tape (registered trademark) (LP-12, manufactured by Nichiban Co., Ltd.) was applied to the solid image surface of the printed sample after being left, and the cello tape (registered trademark) was peeled off after 5 seconds. Then, the cellotape (registered trademark) peeled off from the sample was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

-Evaluation criteria for adhesion-
A: Adherence of color to the cello tape (registered trademark) was not recognized, and deterioration of the solid image of the print sample was not observed.
B: Slight adhesion of the color to the cello tape (registered trademark) was observed, but no deterioration of the solid image of the print sample was observed.
C: Color adhered to an area of less than half of the cello tape (registered trademark), and deterioration of the solid image of the print sample was also observed.
D: Color adhered to more than half the area of Cellotape (registered trademark), and the solid image of the print sample was dropped.
* D is a level that is problematic in practice.

<Hue fluctuation and optical density of image>
Except that the halftone dot density of the image was variously changed, a gray image was formed for each 10% from 10% to 100% halftone dot density in the same manner as the above image formation.
The L *, a *, and b * values (L * ₁ , a * ₁ , b * ₁ ) of each obtained gray image were measured with a spectroscan manufactured by Gretag Macbeth. Similarly, L *, a *, b * values (L * ₂ , a * ₂ , b * ₂ ) of the non-image area were also measured.
From these measured values, the color difference (ΔEab) from the non-image portion was calculated for each gray image by the following formula.
ΔEab = {(a * ₁ −a * ₂ ) ² + (b * ₁ −b * ₂ ) ² } ^1/2
Next, the fluctuation of ΔEab in each gray image (absolute value of the difference between the maximum value and the minimum value) was obtained, and the hue fluctuation of the image was evaluated according to the following evaluation criteria.
Further, the optical density (OD) of the image was measured for an image having a dot density of 100%.
Table 1 shows the evaluation results of the hue fluctuation of the image and the optical density of the image having a dot density of 100%.

-Evaluation criteria for image hue fluctuation-
A: The variation in ΔEab was smaller than 2 and the hue variation was small and good.
B: The variation of ΔEab was 2 or more and less than 4 and was practically acceptable.
C: The variation of ΔEab was 4 or more and less than 6 and was practically unacceptable.
D: The variation in ΔEab was 6 or more, and the hue variation was remarkable.

As shown in Table 1, the average primary particle diameter of the carbon black pigment is 35 nm or more, the content ratio of the carbon black pigment is 60% by mass or more with respect to the total amount of all pigments, and the total amount of all pigments is black. In Examples where the amount was 4% by mass or less with respect to the total amount of the ink composition, the hue variation was suppressed, and the adhesion and abrasion resistance were excellent.
On the other hand, in the ink 2 (comparative example) in which the total amount of all the pigments exceeds 4% by mass with respect to the total amount of the black ink composition, the hue variation increased, and the adhesion and abrasion resistance decreased.
Further, in the ink 3 (comparative example) in which the content ratio of the carbon black pigment is less than 60% by mass with respect to the total amount of all the pigments, the hue variation increased.
Further, in the ink 4 (comparative example) and the ink 5 (comparative example) in which the average primary particle diameter of the carbon black pigment is less than 35 nm, the hue fluctuation increased and the adhesion decreased.

Claims (12)

Carbon black pigment, at least one color pigment selected from magenta pigment and cyan pigment, a water-soluble polymerizable compound, a polymerization initiator, and water,
The carbon black pigment has an average primary particle size of 35 nm or more,
The content ratio of the carbon black pigment is 60% by mass or more and 90% by mass or less with respect to the total amount of all pigments,
A black ink composition for ink jet recording, wherein the total amount of all pigments is 1.5% by mass or more and 4% by mass or less based on the total amount of the black ink composition.   2. The black ink composition according to claim 1, wherein at least a part of the surface of the carbon black pigment and the at least one color pigment is coated with a resin having a salt-forming group.   The black ink composition according to claim 1, wherein the water-soluble polymerizable compound includes a polyfunctional polymerizable compound and a monofunctional polymerizable compound having a (meth) acrylamide structure.   The black ink composition according to claim 2 or 3, wherein the resin having a salt-forming group is crosslinked by a crosslinking agent.   The black ink composition according to any one of claims 2 to 4, wherein the resin having a salt-forming group has at least one of an aromatic ring structure and an alicyclic structure. The black ink composition according to any one of claims 1 to 5, wherein the polymerization initiator is a compound represented by the following general formula (1).

[Wherein, m and n each independently represents an integer of 0 or more, and m + n represents an integer of 0 to 3]   The black ink composition according to any one of claims 1 to 6, further comprising an acetylene glycol surfactant.   The black ink composition according to any one of claims 1 to 7, wherein the total amount of all pigments is 1.8% by mass or more based on the total amount of the black ink composition. The black ink composition according to any one of claims 1 to 8 , wherein the carbon black pigment has a DBP absorption amount of 50 ml / 100 g or more and 150 ml / 100 g or less. The black ink composition according to any one of claims 1 to 9 ,
A treatment liquid containing an aggregating agent capable of forming an aggregate by contact with the black ink composition;
An ink set for ink-jet recording, comprising: The ink set according to claim 10 , wherein the flocculant is an acidic compound. An ink set according to claim 10 or claim 11 is used,
A treatment liquid application step of applying the treatment liquid to a recording medium;
An ink application step of applying the black ink composition to a recording medium;
A curing step of irradiating the image formed by the treatment liquid applying step and the ink applying step with an active energy ray to cure the image;
An image forming method comprising: