JP2009226810A - Ink set for inkjet recording, inkjet recording method, and recorded object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set for inkjet recording which can suppress color material migration in an ink composition after ink dropping and can record a multiple colored image excellent in color density and color hue, and an inkjet recording method. <P>SOLUTION: The ink set includes a water-based ink composition containing a water insoluble color material, a hydrophilic organic solvent, a surfacactant and water and containing 6 mass% of solid contents to polymer particles, a first processing liquid that can form a flocculate when getting into contact with the water-based ink composition, and a second processing liquid having polymer particles, a hydrophilic organic solvent, a surfactant and water and containing a color material of below 0.1 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ink set for ink jet recording, an ink jet recording method using the ink set, and a recorded matter.

  Various recording media have been studied as recording media for inkjet recording, and a technique capable of forming high-quality images is required. Also, various ink materials have been studied for inks from the viewpoints of water resistance and light resistance.

  For example, a pigment is widely used for a colorant that is one of the components of the ink material, and the pigment is used by being dispersed in a medium such as water. When pigments are used in a dispersed manner, the dispersed particle size when dispersed, the stability after dispersion, size uniformity, etc., and ejection properties from the ejection head are important. It is done.

  On the other hand, when recording on plain paper or the like, sufficient performance may not be obtained in terms of fixability (for example, scratch resistance) and resolution in addition to the color density. In particular, there is a case where the speed of ink-jet recording is increased, and there is a demand for recording suitability in the case of performing high-speed recording by a single pass method capable of recording by one head operation instead of the shuttle scan method.

As a technique related to the above, a process of printing an image on an inkjet recording medium using a pigment ink and a process of heating and pressurizing the formed image are provided, and a resin (latex) is applied to at least a part of the image area. ) And a liquid containing substantially no colorant is formed to form an image (see, for example, Patent Document 1). Also disclosed is an ink jet recording method in which a reaction liquid containing a reactant and an ink composition containing a resin emulsion and / or an inorganic oxide colloid are attached to perform printing on a recording medium (for example, Patent Document 2).
JP 2004-181803 A Japanese Patent No. 3550637

  However, the inkjet image forming method in which a liquid containing a resin (latex) is applied to at least a part of the former image area cannot aggregate the pigment ink, so that high-speed printing typified by line printing is performed. It is difficult to carry out, and if a latex-containing liquid is simply applied afterwards, transfer (offset) to the pressure member occurs when a heating and pressing step is subsequently applied.

  Further, in the latter ink jet recording method in which the reaction liquid and the ink composition containing a resin emulsion or the like are attached, it is said that good printing is realized by adding resin fine particles to the ink composition. However, in actuality, after the treatment liquid that can be aggregated by reacting with the ink is attached to the recording medium, the first color ink containing the resin emulsion is printed, and then the colored second color ink is ejected. Then, a phenomenon called color material movement in which the second color ink moves from a predetermined landing position occurs. When the color material moves, unevenness in density and hue occurs in a so-called secondary color image in which red, green, blue, and the like are mixed. Although details are unknown, the movement of the color material is caused by the fact that the ink of the first color causes the water or solvent in the ink to remain as a result of the agglomerated film, and the ink of the second color is ejected onto the liquid film. It is considered that the ink becomes easy to move.

  The present invention has been made in view of the above, and an ink set for ink jet recording and an ink jet capable of suppressing the movement of a color material after a water-based ink composition has landed and recording an image having a good color density and hue. It is an object of the present invention to provide a recording method and a recorded matter on which a multicolor image having a good color density and hue is recorded, and to achieve the object.

  The present invention has a configuration in which polymer particles are not mixed with an ink composition containing a colorant and polymer particles can be applied separately from the ink composition responsible for the formation of a visible image. The use of agglomeration has been achieved on the basis of the knowledge that it is possible to avoid density unevenness and hue unevenness of an image composed of a plurality of colors while adapting to high-speed recording.

Specific means for achieving the above object are as follows.
<1> A water-based ink composition comprising a water-insoluble colorant, a hydrophilic organic solvent, a surfactant, and water, wherein the content of polymer particles is 6% by mass or less of the solid content, and the water-based ink composition A second treatment liquid containing a first treatment liquid capable of forming an aggregate when contacted, polymer particles, a hydrophilic organic solvent, a surfactant, and water, and a colorant content of 0.1% by mass or less; An ink set for ink jet recording including a treatment liquid.

<2> The ink set for ink-jet recording according to <1>, wherein the polymer particles in the second treatment liquid are self-dispersing polymer particles.
<3> The polymer particles in the second treatment liquid are synthesized in an organic solvent, and are prepared as a polymer dispersion having water as a continuous phase by neutralizing part or all of anionic groups. The ink set for inkjet recording according to <1> or <2>, wherein the ink set is for ink jet recording.
<4> The ink set for inkjet recording according to any one of <1> to <3>, wherein the polymer particles in the second treatment liquid are acrylic resin particles. .

<5> The ink jet recording according to any one of <1> to <4>, wherein the water-insoluble colorant in the water-based ink composition is a pigment coated with a polymer dispersant. Ink set.
<6> The ink set for inkjet recording according to <5>, wherein the polymer dispersant is an acrylic polymer.
<7> The ink set for inkjet recording according to any one of <1> to <6>, wherein the first treatment liquid includes a compound having a carboxyl group or a salt thereof.

  <8> A water-based ink composition containing a water-insoluble colorant, a hydrophilic organic solvent, a surfactant, and water, and having a polymer particle content of 6% by mass or less on a recording medium by an inkjet method. An ink applying step for applying, a first processing liquid applying step for applying a first processing liquid capable of forming an aggregate on contact with the aqueous ink composition onto a recording medium, polymer particles, a hydrophilic organic solvent, A second treatment liquid application step of applying a second treatment liquid containing a surfactant and water and having a coloring material content of 0.1% by mass or less onto the recording medium. .

<9> After applying the first treatment liquid on the recording medium in the first treatment liquid application step, the ink application step is provided to apply the aqueous ink composition, and at least the applied aqueous ink composition is applied. The inkjet recording method according to <8>, wherein the second processing liquid is applied in the second processing liquid application step.
<10> Having the ink application step after the first treatment liquid application step,
A heating drying step of heating and drying the first processing liquid on the recording medium after applying the first processing liquid on the recording medium and before applying the aqueous ink composition is provided. The inkjet recording method according to <8> or <9>.

<11> The ink jet recording method according to any one of <8> to <10>, wherein the ink application step applies the water-based ink composition by a line method.
<12> The recording medium according to any one of <8> to <11>, wherein the recording medium has a water absorption coefficient Ka of 0.05 to 0.5 mL / m ² · ms ^1/2. The inkjet recording method described in 1.
<13> A recorded matter recorded by the inkjet recording method according to any one of <8> to <12>.

  According to the present invention, an ink set for ink jet recording and an ink jet recording method capable of suppressing color material movement after the water-based ink composition has landed and recording an image having a good color density and hue, and the color density and It is possible to provide a recorded matter on which a multicolor image having a good hue is recorded.

  Hereinafter, the ink set for ink jet recording of the present invention, the ink jet recording method using the ink set, and the recorded matter will be described in detail.

<Ink set for inkjet recording>
The ink set for inkjet recording of the present invention contains a water-insoluble colorant, a hydrophilic organic solvent, a surfactant, and water, and a water-based ink composition having a polymer particle content of 6% by mass or less. A first treatment liquid capable of forming an aggregate when contacted with an aqueous ink composition, polymer particles, a hydrophilic organic solvent, a surfactant, and water, and a colorant content of 0.1 mass % Of the second processing liquid, and the aqueous ink composition is imaged by causing aggregation when contacting with the first processing liquid.
The ink set for inkjet recording of the present invention may be in a form containing one kind each of the aqueous ink composition, the first treatment liquid, and the second treatment liquid, or in a form containing a plurality of kinds in one or two or more. There may be.

  Conventionally, when recording a multicolor image using two or more types of water-based ink composition, a water-based ink composition in which polymer particles such as latex are mixed with a color material such as a pigment is finally formed into a film with the polymer particles. For example, when an image of the second color or the third color is recorded so as to have a contact or overlapping region after the first color image is recorded, for example, on the first color image Color material movement occurs, and density unevenness, color unevenness, and the like are conspicuous in the final image, which tends to hinder image quality improvement. In the present invention, the polymer particles are used as a separate liquid from the water-based ink composition without containing the polymer particles in the water-based ink composition containing the coloring material, and are placed on the recording medium at a timing different from that of the water-based ink composition. By applying, when multiple types of water-based ink composition are applied on the same recording medium and a multicolor image is recorded, it tends to occur when the plurality of types of water-based ink composition contact or overlap on the recording medium. The movement of the color material can be suppressed, and an image having a good color density and hue can be recorded.

-Water-based ink composition-
The water-based ink composition contains a water-insoluble colorant, a hydrophilic organic solvent, a surfactant, and water, and is configured using other components such as other additives as necessary. be able to. Hereinafter, each component constituting the water-based ink composition will be described in detail.

(Water-insoluble colorant)
The water-based ink composition in the invention contains at least one water-insoluble colorant. By containing a water-insoluble colorant, ink colorability is improved, and a visible image with good color density and hue can be recorded.
The water-insoluble colorant refers to a colorant that is almost insoluble or hardly soluble in water, and specifically means that the amount dissolved in water at 25 ° C. is 0.5% by mass or less. .

As the color material component constituting the water-insoluble color material, known dyes, pigments and the like can be used without particular limitation. Specific examples include various pigments, disperse dyes, oil-soluble dyes, dyes forming J aggregates, and the like, and pigments are more preferable.
In the present invention, a water-insoluble pigment itself or a water-insoluble pigment surface-treated with a dispersant can be contained as a water-insoluble colorant.

The type of the pigment is not particularly limited, and conventionally known organic and inorganic pigments can be used. For example, polycyclic pigments such as azo lakes, azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolinone pigments, quinophthaloni pigments, basic Examples include dye lakes such as dye-type lakes and acid dye-type lakes, organic pigments such as nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments, and inorganic pigments such as titanium oxide, iron oxide, and carbon black. Further, any pigment that is not described in the color index can be used as long as it is dispersible in the aqueous phase. Further, pigments whose surface is treated with a surfactant, a polymer dispersant, or the like, or graft carbon can also be used.
Of these pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, and carbon black pigments are particularly preferable.

Specific examples of the organic pigment used in the present invention are shown below.
Examples of organic pigments for orange or yellow 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.

  Examples of organic pigments for magenta or red 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 222C. I. Pigment violet 19 and the like.

  Examples of organic pigments for green or cyan 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.

  Examples of organic pigments for black include C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7 and the like.

~ Dispersant ~
When a pigment is contained as a coloring material, it is preferably dispersed in an aqueous solvent by a dispersant. The dispersant may be a polymer dispersant or a low molecular surfactant type dispersant. Further, the polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.

  The low molecular surfactant type dispersant (hereinafter sometimes referred to as “low molecular dispersant”) can stably disperse an organic pigment in an aqueous solvent while maintaining a low viscosity of the ink. The low molecular dispersant herein is a low molecular dispersant having a molecular weight of 2000 or less. Moreover, 100-2000 are preferable and, as for the molecular weight of a low molecular dispersing agent, 200-2000 are more preferable.

  The low molecular weight dispersant has a structure including a hydrophilic group and a hydrophobic group. In addition, the hydrophilic group and the hydrophobic group may be independently contained in one molecule or more, and may have a plurality of types of hydrophilic groups and hydrophobic groups. In addition, a linking group for linking a hydrophilic group and a hydrophobic group can be appropriately included.

Examples of the hydrophilic group include an anionic group, a cationic group, a nonionic group, and a betaine type combining these.
The anionic group is not particularly limited as long as it has a negative charge, but may be a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, or a carboxylic acid group. Preferably, it is a phosphoric acid group or a carboxylic acid group, and more preferably a carboxylic acid group.
The cationic group is not particularly limited as long as it has a positive charge, but is preferably an organic cationic substituent, more preferably a cationic group containing nitrogen or phosphorus, and nitrogen. More preferably, it is a cationic group. Among these, a pyridinium cation or an ammonium cation is particularly preferable.
The nonionic group is not particularly limited as long as it has no negative or positive charge, and examples thereof include polyalkylene oxide, polyglycerin, and a part of sugar unit.

In the present invention, the hydrophilic group is preferably an anionic group from the viewpoint of dispersion stability and aggregation of the pigment.
Moreover, when a low molecular weight dispersing agent has an anionic hydrophilic group, it is preferable that the pKa is 3 or more from a viewpoint of making it contact with an acidic process liquid and promoting aggregation reaction. The pKa of the low molecular dispersant in the present invention is determined experimentally from a titration curve by titrating a solution of 1 mol / L of the low molecular dispersant in a tetrahydrofuran-water = 3: 2 (V / V) solution with an acid or alkaline aqueous solution. It is the value obtained in
Theoretically, if the pKa of the low molecular dispersant is 3 or more, 50% or more of the anionic groups are in a non-dissociated state when in contact with a treatment solution having a pH of about 3. Accordingly, the water solubility of the low molecular weight dispersant is remarkably lowered, and an agglomeration reaction occurs. That is, the aggregation reactivity is improved. From this viewpoint, it is preferable that the low molecular dispersant has a carboxylic acid group as an anionic group.

On the other hand, the hydrophobic group may have any structure such as hydrocarbon, fluorocarbon, and silicone, but is preferably hydrocarbon. Further, these hydrophobic groups may have a linear structure or a branched structure. The hydrophobic group may have a single-chain structure or two or more chain structures, and may have a plurality of types of hydrophobic groups in the case of a structure having two or more chains.
The hydrophobic group is preferably a hydrocarbon group having 2 to 24 carbon atoms, more preferably a hydrocarbon group having 4 to 24 carbon atoms, and still more preferably a hydrocarbon group having 6 to 20 carbon atoms.

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

  Examples of hydrophilic polymer compounds that are chemically modified from natural products include fiber polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starches such as sodium starch glycolate and sodium starch phosphate And seaweed polymers such as propylene glycol alginate and the like.

  Synthetic hydrophilic polymer compounds include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone and polyvinyl methyl ether, acrylic polymers such as polyacrylamide, polyacrylic acid or alkali metal salts thereof, and water-soluble styrene acrylic resins. Resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salt of β-naphthalene sulfonic acid formalin condensate, quaternary ammonium, amino group, etc. And a polymer compound having a cationic functional group salt in the side chain.

  Among these, from the viewpoint of pigment dispersion stability and aggregation, a polymer compound containing a carboxyl group is preferable. For example, an acrylic resin such as a water-soluble styrene acrylic resin, a water-soluble styrene maleic resin, and a water-soluble vinyl naphthalene. High molecular compounds containing a carboxyl group such as an acrylic resin and a water-soluble vinyl naphthalene maleic resin are particularly preferred.

  As the water-insoluble dispersant among the polymer dispersants, a polymer having both a hydrophobic part and a hydrophilic part can be used. For example, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer, polyethylene glycol ( Examples thereof include a meth) acrylate- (meth) acrylic acid copolymer and a styrene-maleic acid copolymer.

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

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

In the case where a dye is used as the coloring material, a material in which the dye is held on a water-insoluble carrier can be used as the water-insoluble colored particles. As the dye, known dyes can be used without particular limitation. For example, the dyes described in JP-A-2001-115066, JP-A-2001-335714, JP-A-2002-249677 and the like can be used in the present invention. It can be used suitably. The carrier is not particularly limited as long as it is insoluble in water or hardly soluble in water, and inorganic materials, organic materials, and composite materials thereof can be used. Specifically, the carriers described in JP-A-2001-181549, JP-A-2007-169418, etc. can be suitably used in the present invention.
The carrier holding the dye (water-insoluble colored particles) can be used as an aqueous dispersion using a dispersant. As the dispersant, the above-described dispersants can be suitably used.

The colorant preferably includes a pigment and a dispersant, more preferably includes an organic pigment and a polymer dispersant, and includes a polymer dispersant including an organic pigment and a carboxyl group, from the viewpoint of image light resistance and quality. It is particularly preferred that Among them, the water-insoluble colorant is preferably a water-insoluble colorant in which the colorant (preferably pigment) is coated with a polymer dispersant (preferably having a carboxyl group) from the viewpoint of cohesiveness and eventually ink fixability. Furthermore, a water-insoluble pigment in which a pigment is coated with an acrylic polymer is preferable. As the acrylic polymer, for example, an acrylic resin such as a water-soluble styrene acrylic resin, a water-soluble styrene maleic acid resin, a water-soluble vinyl naphthalene acrylic resin, and a water-soluble vinyl naphthalene maleic resin are preferable.
Furthermore, from the viewpoint of cohesiveness, it is preferable that the acid value of the polymer dispersant is larger than the acid value of the polymer particles (preferably self-dispersing polymer particles) described later.

The average particle diameter of the color material is preferably 10 to 200 nm, more preferably 10 to 150 nm, and still more preferably 10 to 100 nm. When the average particle size is 200 nm or less, the color reproducibility is good, the droplet ejection characteristics when droplets are ejected by the ink jet method are good, and when it is 10 nm or more, the light resistance is good. Further, the particle size distribution of the color material is not particularly limited, and may be either a wide particle size distribution or a monodisperse particle size distribution. Two or more color materials having a monodisperse particle size distribution may be mixed and used.
The average particle size and particle size distribution of the polymer particles are determined by measuring the volume average particle size by a dynamic light scattering method using a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso Co., Ltd.). It is

The content of the water-insoluble colorant in the aqueous ink composition is preferably 1 to 25% by mass, more preferably 2 to 20% by mass with respect to the aqueous ink composition from the viewpoint of image density. 5-20 mass% is further more preferable, and 5-15 mass% is especially preferable.
You may use a water-insoluble coloring material individually by 1 type or in combination of 2 or more types.

(Hydrophilic organic solvent)
The water-based ink composition in the invention contains water as a solvent, but further contains at least one hydrophilic organic solvent. By containing the hydrophilic organic solvent, drying prevention and penetration promotion can be achieved. When a hydrophilic organic solvent is used as an anti-drying agent, nozzle clogging that may occur due to ink drying at the ink discharge port is effectively prevented when an aqueous ink composition is discharged by an inkjet method to record an image. can do.

In order to prevent drying, a hydrophilic organic solvent having a vapor pressure lower than that of water is preferable. Specific examples of hydrophilic organic solvents suitable for drying prevention include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2 , 6-hexanetriol, acetylene glycol derivative, glycerin, polyhydric alcohols represented by trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ) Lower alkyl ethers of polyhydric alcohols such as ethers, heterocyclic rings such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine, Horan, dimethyl sulfoxide, sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives.
Of these, polyhydric alcohols such as glycerin and diethylene glycol are preferred. Moreover, these may be used individually by 1 type, or may use 2 or more types together. These hydrophilic organic solvents are preferably contained in the aqueous ink composition in an amount of 10 to 50% by mass.

  In order to promote penetration, a hydrophilic organic solvent is preferably used from the viewpoint of allowing the aqueous ink composition to penetrate better into the recording medium. Specific examples of hydrophilic organic solvents suitable for promoting penetration include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, and sodium oleate. And nonionic surfactants. A good effect is obtained when these are contained in the water-based ink composition in an amount of 5 to 30% by mass. These hydrophilic organic solvents are preferably used within a range of addition amounts that do not cause printing / image bleeding and paper loss (print-through).

In addition to the above, the hydrophilic organic solvent can be used for adjusting the viscosity. Specific examples of hydrophilic organic solvents that can be used to adjust the viscosity include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, Cyclohexanol, benzyl alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, Thiodiglycol), glycol derivatives (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) Ter, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, Tylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone).
In addition, you may use a hydrophilic organic solvent individually by 1 type or in mixture of 2 or more types.

(Surfactant)
The aqueous ink composition in the present invention contains at least one surfactant. The surfactant is used as a surface tension adjusting agent. Examples of the surface tension adjusting agent include nonionic surfactants, cationic surfactants, anionic surfactants and betaine surfactants.

The surfactant preferably contains an amount capable of adjusting the surface tension of the water-based ink composition to 20 to 60 mN / m in order to eject droplets well by the ink jet method. Especially, content of surfactant is the quantity which can adjust surface tension to 20-45 mN / m, More preferably, it is quantity which can be adjusted to 25-40 mN / m.
The surface tension of the aqueous ink composition is measured at 25 ° C. by a plate method using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

  Specific examples of surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensation in hydrocarbons. Products, anionic surfactants such as polyoxyethylene alkyl sulfates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxy Nonionic surfactants such as ethylene alkylamine, glycerin fatty acid ester and oxyethyleneoxypropylene block copolymer are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred.

Furthermore, pages (37) to (38) of JP-A-59-157636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.
In addition, fluorine (fluorinated alkyl-based) surfactants, silicone-based surfactants and the like described in JP-A Nos. 2003-322926, 2004-325707, and 2004-309806 are also included. Scratch resistance can also be improved.

  These surface tension modifiers can also be used as antifoaming agents, and fluorine compounds, silicone compounds, chelating agents represented by EDTA, and the like can also be used.

(water)
The water-based ink composition in the invention contains water, but the amount of water is not particularly limited. Especially, the preferable content of water is 10 to 99% by mass, more preferably 30 to 80% by mass, and still more preferably 50 to 70% by mass.

(Other ingredients)
The water-based ink composition in the invention can contain other additives as other components in addition to the above components. The water-based ink composition has a polymer particle content of 6% by mass or less based on the solid content of the water-based ink composition. For example, when the first color image is provided, the second color image is provided. From the viewpoint of preventing the movement of the coloring material in the film surface direction when the second color image recording aqueous ink composition is applied by forming the first color film, the content of the polymer particles is the amount of the aqueous ink composition. It is preferably 4% by mass or less, more preferably 2% by mass or less, and even more preferably (0 (zero) mass%) with respect to the solid content.

  Examples of other additives include antifading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, antiseptics, antifungal agents, pH adjusters, antifoaming agents, viscosity modifiers, dispersants, and dispersion stabilizers. And known additives such as rust preventives and chelating agents. These various additives may be added directly after the ink composition is prepared, or may be added when the ink composition is prepared.

  By containing the ultraviolet absorber, image storability can be improved. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-211141, and JP-A No. 10-2 Cinnamic acid compounds described in JP-A-88106 and the like, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8-501291 Triazine compounds described in the above, Research Disclosure No. The compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners can also be used.

  By containing the anti-fading agent, image storability can be improved. As the antifading agent, various organic and metal complex antifading agents can be used. Examples of organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. There are nickel complexes and zinc complexes. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in Japanese Patent No. 15162 and the compounds represented by the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the water-based ink composition in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, a neutralizer (organic base, inorganic alkali) can be used. From the viewpoint of improving the storage stability of the water-based ink composition, the pH adjuster is preferably added so that the pH of the water-based ink composition is 6 to 10, and is preferably added so that the pH is 7 to 10. More preferred.

The viscosity of the water-based ink composition in the present invention is preferably in the range of 1 to 30 mPa · s from the viewpoint of ejection stability when ejected by an ink jet method and an aggregation rate when using a treatment liquid described later. The range of 20 mPa · s is more preferable, the range of 2 to 15 mPa · s is more preferable, and the range of 2 to 10 mPa · s is particularly preferable.
The viscosity is measured using a VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD) under the condition of an aqueous ink composition at 20 ° C.

-First treatment liquid-
The first treatment liquid is a water-based ink composition capable of forming an aggregate when it comes into contact with the water-based ink composition. Specifically, when mixed with the water-based ink composition, the first treatment liquid is a color in the water-based ink composition. It contains at least an aggregating component capable of aggregating dispersed particles such as material particles (pigment or the like) to form an aggregate, and may be configured using other components as necessary. By using the first treatment liquid together with the water-based ink composition, it is possible to speed up ink jet recording, and an image with high density and resolution can be obtained even when recording at high speed.

(Aggregating component)
The first treatment liquid contains at least one aggregation component capable of forming an aggregate upon contact with the aqueous ink composition. By mixing the first treatment liquid with the water-based ink composition ejected by the inkjet method, aggregation of pigments and the like stably dispersed in the water-based ink composition is promoted.

Examples of the first treatment liquid include a liquid capable of generating an aggregate by changing the pH of the aqueous ink composition. At this time, the pH (25 ° C. ± 1 ° C.) of the first treatment liquid is preferably 1 to 6, more preferably 1.2 to 5, from the viewpoint of the aggregation rate of the aqueous ink composition. More preferably, it is 1.5-4. In this case, the pH (25 ± 1 ° C.) of the water-based ink composition used in the ejection process is preferably 7.5 to 9.5 (more preferably 8.0 to 9.0).
Among them, in the present invention, from the viewpoint of image density, resolution, and speedup of inkjet recording, the pH (25 ° C.) of the aqueous ink composition is 7.5 or more, and the pH of the first treatment liquid (25 (C) is preferably 3-5.
The aggregating components can be used alone or in combination of two or more.

  A 1st process liquid can be comprised using at least 1 sort (s) of an acidic compound as an aggregation component. As the acidic compound, a compound having a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, or a carboxyl group, or a salt thereof (for example, a polyvalent metal salt) may be used. it can. Among these, from the viewpoint of the aggregation rate of the aqueous ink composition, a compound having a phosphate group or a carboxyl group is more preferable, and a compound having a carboxyl group is still more preferable.

  The compound having a carboxyl group includes polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid. , Pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, derivatives of these compounds, or salts thereof (for example, polyvalent metal salts), etc. It is preferable to be selected from among These compounds may be used alone or in combination of two or more.

The 1st process liquid in this invention can further comprise the aqueous solvent (for example, water) in addition to the said acidic compound.
As content of the acidic compound of a 1st process liquid, it is preferable that it is 5-95 mass% with respect to the total mass of a 1st process liquid from a viewpoint of the aggregation effect, and it is 10-80 mass%. More preferable

  Further, as a preferred example of the first treatment liquid for improving the high-speed aggregation property, a first treatment liquid to which a polyvalent metal salt or polyallylamine is added can be mentioned. 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 cations from Group 13 of the periodic table. (For example, aluminum), salts of lanthanides (for example, neodymium), polyallylamine, and polyallylamine derivatives. As the metal salt, 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.

  As content in the 1st process liquid of a metal salt, 1-10 mass% is preferable, More preferably, it is 1.5-7 mass%, More preferably, it is the range of 2-6 mass%.

The viscosity of the first treatment liquid is preferably in the range of 1 to 30 mPa · s, more preferably in the range of 1 to 20 mPa · s, and further in the range of 2 to 15 mPa · s from the viewpoint of the aggregation rate of the aqueous ink composition. A range of 2 to 10 mPa · s is particularly preferable. The viscosity is measured under a condition of 20 ° C. using VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
The surface tension of the first treatment liquid is preferably 20 to 60 mN / m, more preferably 20 to 45 mN / m, more preferably 25 to 40 mN / m from the viewpoint of the aggregation speed of the aqueous ink composition. More preferably, it is m. The surface tension is measured under conditions of 25 ° C. using an Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

-Second treatment liquid-
The second treatment liquid contains at least polymer particles, a hydrophilic organic solvent, a surfactant, and water, and can be configured using other components as necessary. In the second treatment liquid, the content of the color material being 0.1% by mass or less means that the color material is not substantially contained as a coloring component, and preferably in the second treatment liquid. The color material content is 0 (zero).

For details and preferred embodiments of the hydrophilic organic solvent, surfactant, and water contained in the second treatment liquid, the hydrophilic organic solvent, surfactant, and water contained in the aqueous ink composition described above are used. Same as water.
Hereinafter, the polymer particles contained in the second treatment liquid will be described in detail.

The second treatment liquid of the present invention contains at least one polymer particle. Examples of polymer particles include thermoplastic, thermosetting or modified acrylic, epoxy, polyurethane, polyether, polyamide, unsaturated polyester, phenol, silicone, or fluorine resins, chloride Amino resins such as polyvinyl resins such as vinyl, vinyl acetate, polyvinyl alcohol or polyvinyl butyral, polyester resins such as alkyd resins and phthalic resins, melamine resins, melamine formaldehyde resins, aminoalkyd co-condensation resins, urea resins, urea resins, etc. Examples thereof include polymer particles of a resin having an anionic group such as a system material, a copolymer or a mixture thereof.
Of these, anionic acrylic resin particles are preferred. Anionic acrylic resin, for example, polymerizes an acrylic monomer having an anionic group (anionic group-containing acrylic monomer) and, if necessary, other monomers copolymerizable with the anionic group-containing acrylic monomer in a solvent Is obtained. Examples of the anionic group-containing acrylic monomer include an acrylic monomer having one or more selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic group. Among them, an acrylic monomer having a carboxyl group (for example, acrylic acid) Methacrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid and the like), and acrylic acid or methacrylic acid is particularly preferred.

  The polymer particles in the present invention are preferably self-dispersing polymer particles having a carboxyl group from the viewpoint of ejection stability and liquid stability (particularly dispersion stability) when a colorant (particularly pigment) described later is used. Self-dispersing polymer particles are more preferred. Self-dispersing polymer particles are water-insoluble polymers that can be dispersed in an aqueous medium by the functional groups (particularly acidic groups or salts thereof) of the polymer itself in the absence of other surfactants, By means of water-insoluble polymer particles containing no free emulsifier.

Here, the dispersed state refers to both 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 in a solid state. It includes the state of.
The water-insoluble polymer in the present invention is preferably a water-insoluble polymer that can be in a dispersed state in which the water-insoluble polymer is dispersed in a solid state, from the viewpoint of aggregation speed and fixability when an aqueous ink composition is used.

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

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

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

  The main chain skeleton of the water-insoluble polymer is not particularly limited. For example, a vinyl polymer or a condensation polymer (epoxy resin, polyester, polyurethane, polyamide, cellulose, polyether, polyurea, polyimide, polycarbonate, etc.) is used. it can. Of these, vinyl polymers are particularly preferred.

Preferable examples of the vinyl polymer and the monomer constituting the vinyl polymer include those described in JP-A Nos. 2001-181549 and 2002-88294. In addition, radical transfer of vinyl monomers using dissociable groups (or substituents that can be induced to dissociable groups), polymerization initiators, and iniferters, or dissociable groups on either initiators or terminators A vinyl polymer in which a dissociable group is introduced at the end of a polymer chain by ionic polymerization using a compound having (or a substituent that can be derived from a dissociable group) can also be used.
Moreover, as a suitable example of the monomer which comprises a condensation type polymer and a condensation type polymer, what is described in Unexamined-Japanese-Patent No. 2001-247787 can be mentioned.

  The self-dispersing polymer particles in the present invention preferably contain a water-insoluble polymer containing a hydrophilic constituent unit and a constituent unit derived from an aromatic group-containing monomer from the viewpoint of self-dispersibility.

The hydrophilic structural unit is not particularly limited as long as it is derived from a hydrophilic group-containing monomer, and even if it is derived from one kind of hydrophilic group-containing monomer, it contains two or more hydrophilic groups. It may be derived from a monomer. The hydrophilic group is not particularly limited, and may be a dissociable group or a nonionic hydrophilic group.
In the present invention, the hydrophilic group is preferably a dissociable group and more preferably an anionic dissociable group from the viewpoint of promoting self-dispersion and the stability of the formed emulsified or dispersed state. Examples of the dissociable group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among them, a carboxyl group is preferable from the viewpoint of fixability when an ink composition is configured.

The hydrophilic group-containing monomer in the present invention is preferably a dissociable group-containing monomer from the viewpoints of self-dispersibility and aggregation, and is a dissociable group-containing monomer having a dissociable group and an ethylenically unsaturated bond. It is preferable.
Examples of the dissociable group-containing monomer include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.

Specific examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid. Specific examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-sulfopropyl (meth) acrylate, and bis- (3-sulfopropyl) -itaconate. It is done. Specific examples of unsaturated phosphoric acid monomers include vinylphosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2- Examples include acryloyloxyethyl phosphate.
Among the dissociable group-containing monomers, unsaturated carboxylic acid monomers are preferable and acrylic acid and methacrylic acid are more preferable from the viewpoints of dispersion stability and ejection stability.

The self-dispersing polymer particles in the present invention preferably contain a polymer having a carboxyl group from the viewpoint of self-dispersibility and agglomeration speed when contacted with the treatment liquid, and have a carboxyl group and an acid value (mgKOH / g It is more preferable that the polymer contains 25-100. Furthermore, the acid value is more preferably from 25 to 80, and particularly preferably from 30 to 65, from the viewpoints of self-dispersibility and the aggregation rate when contacted with the treatment liquid.
In particular, when the acid value is 25 or more, the stability of self-dispersibility is good, and when it is 100 or less, the cohesiveness is improved.

The aromatic group-containing monomer is not particularly limited as long as it is a compound containing an aromatic group and a polymerizable group. The aromatic group may be a group derived from an aromatic hydrocarbon or a group derived from an aromatic heterocycle. In the present invention, an aromatic group derived from an aromatic hydrocarbon is preferable from the viewpoint of particle shape stability in an aqueous medium.
The polymerizable group may be a condensation polymerizable polymerizable group or an addition polymerizable polymerizable group. In the present invention, from the viewpoint of particle shape stability in an aqueous medium, an addition polymerizable group is preferable, and a group containing an ethylenically unsaturated bond is more preferable.

  The aromatic group-containing monomer in the present invention is preferably a monomer having an aromatic group derived from an aromatic hydrocarbon and an ethylenically unsaturated bond. The aromatic group-containing monomer may be used alone or in combination of two or more.

Examples of the aromatic group-containing monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and a styrene monomer. Of these, aromatic group-containing (meth) acrylate monomers are preferred from the viewpoint of the balance between the hydrophilicity and hydrophobicity of the polymer chain and the ink fixability, and include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth). At least one selected from acrylates is more preferable, and phenoxyethyl (meth) acrylate and benzyl (meth) acrylate are more preferable.
“(Meth) acrylate” means acrylate or methacrylate.

The self-dispersing polymer particles in the present invention are preferably acrylic polymer particles, include structural units derived from an aromatic group-containing (meth) acrylate monomer, and the content thereof is 10% by mass to 95% by mass. Preferably there is. When the content of the aromatic group-containing (meth) acrylate monomer is 10% by mass to 95% by mass, the stability of the self-emulsification or dispersion state can be improved, and further the increase in ink viscosity can be suppressed.
In the present invention, from the viewpoints of stability in a self-dispersing state, stabilization of particle shape in an aqueous medium due to hydrophobic interaction between aromatic rings, and reduction in the amount of water-soluble components due to appropriate hydrophobicization of particles. More preferably, the content is from mass% to 90 mass%, more preferably from 15 mass% to 80 mass%, and particularly preferably from 25 mass% to 70 mass%.

  The self-dispersing polymer particles in the present invention can be constituted using, for example, a structural unit derived from an aromatic group-containing monomer and a structural unit derived from a dissociable group-containing monomer. Furthermore, other structural units may be further included as necessary.

The monomer that forms the other structural unit is not particularly limited as long as it is a monomer copolymerizable with the aromatic group-containing monomer and the dissociable group-containing monomer. Among these, an alkyl group-containing monomer is preferable from the viewpoint of flexibility of the polymer skeleton and ease of control of the glass transition temperature (Tg).
Examples of the alkyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, alkyl (meth) acrylates such as t-butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Ethylenically unsaturated monomers having a hydroxyl group such as acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate; Dialkylaminoalkyl (meth) acrylates such as ru (meth) acrylate; N-hydroxyalkyl (meth) such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide Acrylamide; N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- (n-, iso) butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meta And (meth) acrylamides such as N-alkoxyalkyl (meth) acrylamides such as acrylamide and N- (n-, iso) butoxyethyl (meth) acrylamide.

  The molecular weight range of the water-insoluble polymer constituting the self-dispersing polymer particles in the present invention is preferably 3000 to 200,000, more preferably 5000 to 150,000, and more preferably 10,000 to 100,000 in terms of weight average molecular weight. More preferably it is. By setting the weight average molecular weight to 3000 or more, the amount of water-soluble components can be effectively suppressed. Moreover, self-dispersion stability can be improved by making a weight average molecular weight into 200,000 or less.

  The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran) as an eluent. ) Is used. The conditions are as follows: the sample concentration is 0.35 / min, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and an IR detector is used. In addition, the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, It is prepared from 8 samples of “A-2500”, “A-1000”, “n-propylbenzene”.

The water-insoluble polymer constituting the self-dispersing polymer particle in the present invention is a structural unit derived from an aromatic group-containing (meth) acrylate monomer (preferably phenoxyethyl (meth) acrylate) from the viewpoint of controlling the hydrophilicity / hydrophobicity of the polymer. It is preferable that 15-80 mass% of the total mass of a self-dispersing polymer particle is included as a copolymerization ratio for the structural unit derived from and / or the structural unit derived from benzyl (meth) acrylate.
In addition, the water-insoluble polymer has an anionic group (preferably a carboxyl group) as a copolymerization ratio of a structural unit derived from an aromatic group-containing (meth) acrylate monomer from the viewpoint of controlling hydrophilicity / hydrophobicity of the polymer. It is preferable to include a structural unit derived from a containing monomer and a structural unit derived from an alkyl group-containing monomer (preferably a structural unit derived from an alkyl ester of (meth) acrylic acid), and phenoxyethyl (meth) acrylate 15 to 80% by mass of a structural unit derived from and / or a structural unit derived from benzyl (meth) acrylate as a copolymerization ratio, a structural unit derived from an anion group (preferably carboxyl group) -containing monomer, and an alkyl group-containing monomer The structural unit derived from (preferably, having 1 to 1 carbon atoms of (meth) acrylic acid It is more preferable that the acid value is 25 to 100 and the weight average molecular weight is 3000 to 200,000, and the acid value is 25 to 25. More preferably, the weight average molecular weight is 95 to 150,000.

  Specific examples of the water-insoluble polymer constituting the self-dispersing polymer particles are listed below as exemplary compounds B-01 to B-19, but the present invention is not limited thereto. In addition, the parenthesis represents the mass ratio of the copolymer component.

B-01: Phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (50/45/5)
B-02: Phenoxyethyl acrylate / benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (30/35/29/6)
B-03: Phenoxyethyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (50/44/6)
B-04: Phenoxyethyl acrylate / methyl methacrylate / ethyl acrylate / acrylic acid copolymer (30/55/10/5)
B-05: benzyl methacrylate / isobutyl methacrylate / methacrylic acid copolymer (35/59/6)
B-06: Styrene / phenoxyethyl acrylate / methyl methacrylate / acrylic acid copolymer (10/50/35/5)
B-07: benzyl acrylate / methyl methacrylate / acrylic acid copolymer (55/40/5)
B-08: Phenoxyethyl methacrylate / benzyl acrylate / methacrylic acid copolymer (45/47/8)
B-09: Styrene / phenoxyethyl acrylate / butyl methacrylate / acrylic acid copolymer (5/48/40/7)
B-10: benzyl methacrylate / isobutyl methacrylate / cyclohexyl methacrylate / methacrylic acid copolymer (35/30/30/5)
B-11: Phenoxyethyl acrylate / methyl methacrylate / butyl acrylate / methacrylic acid copolymer (12/50/30/8)
B-12: benzyl acrylate / isobutyl methacrylate / acrylic acid copolymer (93/2/5)
B-13: Styrene / phenoxyethyl methacrylate / butyl acrylate / acrylic acid copolymer (50/5/20/25)
B-14: Styrene / butyl acrylate / acrylic acid copolymer (62/35/3)
B-15: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/51/4)
B-16: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/49/6)
B-17: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/48/7)
B-18: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/47/8)
B-19: Methyl methacrylate / phenoxyethyl acrylate / acrylic acid copolymer (45/45/10)

  The method for producing the water-insoluble polymer constituting the self-dispersing polymer particles in the present invention is not particularly limited. For example, emulsion polymerization is carried out in the presence of a polymerizable surfactant to obtain a surfactant and a water-insoluble polymer. Examples include a method of covalent bonding, and a method of copolymerizing a monomer mixture containing the hydrophilic group-containing monomer and the aromatic group-containing monomer by a known polymerization method such as a solution polymerization method or a bulk polymerization method. Among the polymerization methods, a solution polymerization method is preferable and a solution polymerization method using an organic solvent is more preferable from the viewpoint of aggregation rate and droplet ejection stability when an ink composition is used.

  The self-dispersing polymer particles in the present invention include a polymer synthesized in an organic solvent from the viewpoint of aggregation rate, and the polymer has an anionic group (preferably a carboxyl group), and preferably has an acid value of 20 to 100) and part or all of anionic groups (for example, carboxyl groups) of the polymer are preferably neutralized and prepared as a polymer dispersion having water as a continuous phase. That is, the production of the self-dispersing polymer particles in the present invention includes a step of synthesizing a polymer in an organic solvent and a dispersion in which at least a part of anionic groups (for example, carboxyl groups) of the polymer is neutralized. It is preferable to provide a process.

The dispersion step preferably includes the following step (1) and step (2).
Step (1): Step of stirring a mixture containing a polymer (water-insoluble polymer), an organic solvent, a neutralizing agent, and an aqueous medium Step (2): Step of removing the organic solvent from the mixture

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

Preferred examples of the organic solvent include alcohol solvents, ketone solvents, and ether solvents.
Examples of the alcohol solvent include isopropyl alcohol, n-butanol, t-butanol, ethanol and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone. Examples of ether solvents include dibutyl ether and dioxane. Among these solvents, ketone solvents such as methyl ethyl ketone and alcohol solvents such as isopropyl alcohol are preferable. It is also preferable to use isopropyl alcohol and methyl ethyl ketone in combination for the purpose of moderating the polarity change during the phase inversion from oil to water. By using this solvent in combination, it is possible to obtain self-dispersing polymer particles having a fine particle size with high dispersion stability without aggregation and sedimentation and fusion between particles.

  The neutralizing agent is used so that a part or all of the dissociable group is neutralized and the self-dispersing polymer forms a stable emulsified or dispersed state in water. When the self-dispersing polymer has an anionic dissociative group (for example, a carboxyl group) as a dissociable group, examples of the neutralizing agent used include basic compounds such as organic amine compounds, ammonia, and alkali metal hydroxides. It is done. Examples of organic amine compounds include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethyl-ethanolamine, N, N-diethyl-ethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, N-methyldiethanolamine, N-ethyldiethanolanine, monoisopropanolamine, di Examples include isopropanolamine and triisopropanolamine. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Among these, sodium hydroxide, potassium hydroxide, triethylamine, and triethanolamine are preferable from the viewpoint of stabilizing the dispersion of the self-dispersing polymer particles of the present invention in water.

  These basic compounds are preferably used in an amount of 5 to 120 mol%, more preferably 10 to 110 mol%, still more preferably 15 to 100 mol%, based on 100 mol% of the dissociable group. . By setting it as 15 mol% or more, the effect which stabilizes dispersion | distribution of the particle | grains in water expresses, and there exists an effect which reduces a water-soluble component by setting it as 100 mol% or less.

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

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

The content of the polymer particles (particularly self-dispersing polymer particles) in the aqueous ink composition is preferably 1 to 30% by mass with respect to the aqueous ink composition from the viewpoint of glossiness of the image, More preferably, it is 5-15 mass%.
The polymer particles (particularly self-dispersing polymer particles) can be used singly or in combination of two or more.

  The ratio (coloring material / polymer particle) between the water-insoluble coloring material contained in the water-based ink composition and the polymer particles (preferably self-dispersing polymer particles) contained in the second processing liquid may be an image scratch resistance. From the viewpoint of properties and the like, it is preferably 1 / 0.5 to 1/10, more preferably 1/1 to 1/4.

<Inkjet recording method>
The ink jet recording method of the present invention includes the ink application step of applying the above-described aqueous ink composition onto a recording medium, and the above-described first treatment liquid capable of forming an aggregate when contacted with the aqueous ink composition. The first treatment liquid application step to be applied on the recording medium and the second treatment liquid application step to apply the second treatment liquid described above to the recording medium are provided at least, and if necessary Thus, other steps can be provided and configured.

The water-based ink composition in the ink jet recording method of the present invention comprises at least a water-insoluble colorant, a hydrophilic organic solvent, a surfactant, and water, and the content of polymer particles is 6 in the solid content of the water-based ink composition. The details and preferred embodiments of each component are as described above. The first treatment liquid can be configured using an aggregating component or the like, and details and preferred aspects of each component are as described above. The second treatment liquid contains at least polymer particles, a hydrophilic organic solvent, a surfactant, and water, and is configured so that the content of the coloring material is 0.1% by mass or less. Details of each component The preferred embodiments are as described above.
In the second treatment liquid, the content of the color material being 0.1% by mass or less means that the color material is not substantially contained as a coloring component, and preferably the color in the second treatment liquid. The material content is 0 (zero).

  In the inkjet recording method of the present invention, when forming a recording system in which a first treatment liquid capable of forming an aggregate with the aqueous ink composition is acted on the color material-containing aqueous ink composition to form an image. In addition, the water-based ink composition containing a coloring material is substantially free of polymer particles, and the polymer particles are used as a separate liquid from the water-based ink composition and contain polymer particles at a different timing from the water-based ink composition. By providing the liquid on the recording medium, it is possible to suppress movement of the coloring material when a plurality of types of water-based ink compositions contact or overlap each other on the same recording medium. Hue is improved.

Hereafter, each process which comprises the inkjet recording method of this invention is demonstrated.
-Ink application process-
In the ink application step, the above-described aqueous ink composition is applied onto a recording medium by an inkjet method. In this step, a water-based ink composition can be selectively applied on the recording medium, and a desired visible image can be formed. The details of the water-based ink composition are as described above.

  Specifically, the image recording using the ink-jet method is performed by supplying energy to obtain a desired recording medium, that is, plain paper, resin-coated paper, for example, JP-A-8-169172 and JP-A-8-27693. Publication No. 2-276670, No. 7-276789, No. 9-323475, No. JP-A-62-238783, JP-A-10-153898, No. 10-217473, No. 10- No. 235995, No. 10-337947, No. 10-217597, No. 10-337947, etc. Liquid composition for ink jet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. This can be done by discharging objects. As a preferable ink jet recording method for the present invention, the method described in paragraph Nos. 0093 to 0105 of JP-A No. 2003-306623 can be applied.

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. As an ink jet method, in particular, the method described in Japanese Patent Application Laid-Open No. Sho 54-59936 causes an abrupt volume change of the ink subjected to the action of thermal energy, and the ink is ejected from the nozzle by the action force due to this state change. Ink jet method can be used effectively.
The ink jet method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the 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 inkjet head, a single 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 in which recording elements are arranged corresponding to the entire area of one side of the recording medium. There is a line system using a head. In the line system, 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 that does not use a dummy jet, the effect of improving ejection accuracy and image scratch resistance is great.

-1st process liquid provision process-
In the first treatment liquid application step, the above-described first treatment liquid capable of forming an aggregate when contacted with the aqueous ink composition is applied on the recording medium, and the aqueous ink composition and the treatment liquid are brought into contact with each other. It can be set as the structure imaged. In this case, when the first treatment liquid comes into contact with, for example, an aqueous ink composition containing pigment particles, the dispersed particles containing the pigment particles in the aqueous ink composition aggregate to fix the image on the recording medium.
Details and preferred embodiments of the first treatment liquid are as described above.

  Application | coating of a 1st process liquid can be performed by applying well-known methods, such as the apply | coating method, the inkjet method, and the immersion method. As a coating method, a known coating method using a bar coater, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater or the like can be used. The details of the inkjet method are as described above.

  The first treatment liquid application step may be provided either before or after the ink application step using the aqueous ink composition and the second treatment liquid application step described later.

  In this invention, the aspect which provided the ink provision process after providing the 1st process liquid at the 1st process liquid provision process is preferable. That is, before applying the water-based ink composition to the recording medium, a first treatment liquid for aggregating the coloring material (preferably pigment) in the water-based ink composition is previously applied, and the recording medium is then applied to the recording medium. A mode in which an aqueous ink composition is applied so as to come into contact with the applied first treatment liquid to form an image 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. In this case, the second treatment liquid application step described later can be provided before the first treatment liquid application step or between the first treatment liquid application step and the ink application step, but the water-based ink composition has landed. From the viewpoint of suppressing the subsequent movement of the coloring material and obtaining a good color density and hue, the second treatment liquid application step is preferably an embodiment provided after the first treatment liquid application step and the ink application step.

-2nd process liquid provision process-
In the second treatment liquid application step, the above-described second treatment liquid is applied onto the recording medium. The second treatment liquid is preferably applied so as to at least overlap with the aqueous ink composition forming an image, and is preferably applied selectively by an ink jet method.
The details of the ink jet method are as described above.

  The application amount of the second treatment liquid varies depending on the image form, but in terms of the application amount of the aqueous ink composition, from the viewpoint of image scratch resistance, the water-insoluble colorant in the aqueous ink composition, 2 The amount between the polymer particles in the treatment liquid (coloring material / polymer particles) is preferably in the range of 1 / 0.5 to 1/10, and the amount in the range of 1/1 to 1/4 Is more preferable.

  In the ink jet recording method of the present invention, the ink application step, the first treatment liquid application step, and the second treatment liquid application step have a large effect of suppressing the movement of the coloring material after the water-based ink composition has landed, It is preferable that the first treatment liquid application step, the ink application step, and the second treatment liquid application step are sequentially performed on the recording medium in that the color density and the hue can be further improved.

  In the present invention, an ink application step is provided after the first treatment liquid application step, and after the first treatment liquid is applied onto the recording medium, the aqueous ink composition is applied until the aqueous ink composition is applied. It is preferable to further provide a heat drying step for heat drying the first treatment liquid. By heating and drying the first 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, a blowing means using blowing air such as a dryer, or a combination of these. As a heating method, for example, a method of applying heat with a heater or the like from the side opposite to the first treatment liquid application surface of the recording medium, a method of applying warm air or hot air to the first treatment liquid application surface of the recording medium, infrared rays The heating method using a heater is mentioned, You may heat combining these two or more.

-Recording media-
The inkjet recording 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 ink jet recording method of the present invention, it is possible to record a high-quality image excellent in color density and hue by suppressing the movement of the color material.

  As the recording medium, commercially available media can be used. For example, “OK Prince fine quality” manufactured by Oji Paper Co., Ltd., “Shiorai” manufactured by Nippon Paper Industries Co., Ltd., and Nippon Paper Industries ( Fine coated paper such as “New NPI fine quality” manufactured by Co., Ltd., “OK Everlight Coat” manufactured by Oji Paper Co., Ltd., and “Aurora S” manufactured by Nippon Paper Industries Co., Ltd., Oji Lightweight coated paper (A3) such as “OK Coat L” manufactured by 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 Kanfuji +” manufactured by Oji Paper Co., Ltd. and “Tokuhishi Art” manufactured by Mitsubishi Paper Industries Co., Ltd. Is 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 hand transfer of water between a contact time of 100 ms and a contact time of 900 ms using KM500Win (manufactured by Kumagai Riki Co., Ltd.).

  Next, an example of forming an image by the ink jet recording medium method of the present invention will be specifically described with reference to FIG. FIG. 1 is a schematic configuration diagram illustrating an example of the overall configuration of an inkjet recording apparatus.

  The ink jet recording apparatus shown in FIG. 1 includes a first processing liquid discharge head 12S that sequentially discharges a first processing liquid containing an aggregating component in the recording medium conveyance direction (arrow direction in the drawing). A treatment liquid application section 12, a treatment liquid drying zone 13 provided with a heating means (not shown) for drying the applied first treatment liquid, an ink discharge section 14 for discharging various aqueous inks and a second treatment liquid, An ink drying zone 15 for drying the discharged water-based ink and the second processing liquid is provided. Further, an image fixing unit 16 for fixing an image on the recording medium is disposed on the downstream side of the ink drying zone 15 in the conveyance direction of the recording medium.

  The recording medium supplied to the ink jet recording apparatus includes a first processing liquid application unit 12, a processing liquid drying zone 13, an ink by a conveyance roller from a paper feeding unit that feeds the recording medium from a case loaded with the recording medium. The ink is sent in the order of the ejection unit 14 and the ink drying zone 15, and further sent to the stacking unit through a fixing process in the image fixing unit 16 as necessary. In addition to the method using a conveyance roller, the conveyance may be performed by a drum conveyance method using a drum-shaped member, a belt conveyance method, a stage conveyance method using a stage, or the like.

  Among the plurality of transport rollers, at least one roller may be a driving roller to which the power of a motor (not shown) is transmitted. By rotating a driving roller rotated by a motor at a constant speed, the recording medium is conveyed in a predetermined direction by a predetermined conveyance amount.

  The first treatment liquid application unit 12 is provided with a first treatment liquid discharge head 12S that is connected to a storage tank that stores the treatment liquid. The first treatment liquid ejection head 12S is configured to eject the treatment liquid from ejection nozzles arranged to face the recording surface of the recording medium, and to apply the treatment liquid onto the recording medium. In addition, the 1st process liquid provision part 12 can also employ | adopt the application | coating system using an application roller not only the system discharged from a nozzle-shaped head. In this coating method, the treatment liquid can be easily applied to almost the entire surface including the image area where the ink droplets land on the recording medium by the ink discharge unit 14 disposed on the downstream side. In order to make the thickness of the processing liquid on the recording medium constant, for example, an air knife or a member having a sharp corner is provided with a gap corresponding to the specified amount of the processing liquid provided between the recording medium and the recording medium. You may provide the method of doing.

  A treatment liquid drying zone 13 is disposed downstream of the first treatment liquid application unit 12 in the recording medium conveyance direction. The treatment liquid drying zone 13 can be configured by using known heating means such as a heater, air blowing means using air blowing such as a dryer, or a combination of these. The heating means may be a method of installing a heating element such as a heater on the side opposite to the barrier layer forming surface of the recording medium (for example, below the conveying mechanism for loading and conveying the recording medium when the recording medium is automatically conveyed) Examples include a method of applying warm air or hot air to the surface of the medium on which the barrier layer is formed, a heating method using an infrared heater, and the like.

In addition, since the surface temperature of the recording medium changes depending on the type (material, thickness, etc.) of the recording medium, the environmental temperature, etc., the measuring unit for measuring the surface temperature of the recording medium and the surface of the recording medium measured by the measuring unit It is preferable to provide a control mechanism that feeds back the temperature value to the heating control unit to form the blocking layer while controlling the temperature. As a measurement part which measures the surface temperature of a recording medium, a contact or non-contact thermometer is preferable.
Further, the solvent may be removed using a solvent removal roller or the like. As another embodiment, a method of removing excess solvent from the recording medium with an air knife is also used.

  The ink discharge unit 14 is disposed downstream of the treatment liquid drying zone 13 in the recording medium conveyance direction. The ink ejection unit 14 includes recording heads (inks) connected to each of the color inks of cyan (C), magenta (M), yellow (Y), and black (K) and the liquid storage unit storing the second processing liquid. Discharge heads 30C, 30M, 30Y, and 30K, and a second treatment liquid discharge head 30A) are disposed. Each liquid storage section (not shown) stores a water-based ink (liquid ink composition) containing a water-insoluble colorant or the like corresponding to each hue, or a second processing liquid containing polymer particles. In addition, the ink discharge heads 30C, 30M, 30Y, and 30K and the second treatment liquid discharge head 30A are supplied.

The ink ejection heads 30C, 30M, 30Y, and 30K each eject an ink composition corresponding to an image from ejection nozzles that are arranged to face the recording surface of the recording medium. The second processing liquid is further discharged from the discharge nozzle of the processing liquid discharge head 30A. In this way, each color ink is applied to the recording surface of the recording medium, and a color image is recorded by applying the second treatment liquid onto at least the applied ink.
At this time, as shown in FIG. 1, the second treatment liquid is applied after all colors of cyan, magenta, yellow, and black are applied, and at the time when a part of the planned ink is applied, for example, selection is performed. Alternatively, the second treatment liquid may be applied.

Each of the first processing liquid discharge head 12S, the ink discharge heads 30C, 30M, 30Y, and 30K, and the second processing liquid discharge head 30A has a maximum recording width (maximum) of an image recorded on the recording medium. A full line head in which a large number of ejection openings (nozzles) are arranged over the recording width). Compared to the serial type in which recording is performed while reciprocating a short shuttle head in the width direction of the recording medium (direction perpendicular to the conveying direction on the recording medium conveying surface), it is possible to record an image on the recording medium at a higher speed. it can. In the present invention, either a serial type recording or a method capable of relatively high-speed recording, for example, a method capable of recording by ejecting in the main scanning direction by a single pass forming one line in one scan. However, according to the image recording method of the present invention, it is possible to obtain a high-quality image with high image reproducibility and excellent scratch resistance while maintaining ejection stability even with a single-pass method.
Here, the first treatment liquid ejection head 12S, the ink ejection heads 30C, 30M, 30Y, and 30K, and the second treatment liquid ejection head 30A all have the same structure.

  The application amount of the first treatment liquid, the application amount of the water-based ink, and the application amount of the second treatment liquid are preferably adjusted as necessary. For example, the application amount of the first treatment liquid may be changed according to the recording medium in order to adjust the physical properties such as the viscoelasticity of the aggregate formed by mixing the first treatment liquid and the aqueous ink. Further, the application amount of the second treatment liquid may be changed according to the components such as the color material content of the water-based ink.

  The ink drying zone 15 is disposed downstream of the ink discharge unit 14 in the recording medium conveyance direction. The ink drying zone 15 can be configured in the same manner as the treatment liquid drying zone 13.

After the image is dried, an image fixing unit 16 may be separately provided as needed to give a strong fixing property to the recording medium.
The image fixing unit 16 is disposed further downstream in the recording medium conveyance direction of the ink drying zone 15. The image fixing unit 16 is provided with a roller pair in which the fixing rollers 40A and 40B are in pressure contact with each other, and an image formed on the recording medium is added by passing the recording medium between the fixing rollers 40A and 40B. The fixability of an image recorded on a recording medium by being pressurized and heated can be improved. The fixing rollers 40A and 40B are preferably a roller pair including one pressure roller and one heating roller, but are not limited thereto.

  Further, in the ink jet recording apparatus, a heating unit that performs a heat treatment on the recording medium can be arranged in a conveyance path from the paper feeding unit to the stacking unit. For example, the temperature of the recording medium is raised to a desired temperature by disposing a heating unit at a desired position such as the upstream side of the treatment liquid drying zone 13 or between the ink discharge unit 14 and the ink drying zone 15. Thus, drying and fixing can be effectively performed.

  In the ink set for ink-jet recording and the ink-jet recording method of the present invention, movement of the coloring material on the same recording medium can be suppressed, so that a recorded matter on which a multicolor image having a good color density and hue is recorded can be obtained.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

  The weight average molecular weight was measured by gel permeation chromatography (GPC). For GPC, HLC-8020GPC (manufactured by Tosoh Corporation) is used, TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns, and THF (tetrahydrofuran) is used as an eluent. ) Was used. The conditions were as follows: the sample concentration was 0.35 / min, the flow rate was 0.35 ml / min, the sample injection amount was 10 μl, the measurement temperature was 40 ° C., and an IR detector was used. In addition, the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, It produced from eight samples of "A-2500", "A-1000", and "n-propylbenzene".

Example 1
<Preparation of first treatment liquid>
The component of the following composition was mixed and the process liquid T-1 (1st process liquid) was prepared. When the viscosity, surface tension, and pH (25 ± 1 ° C.) of the treatment liquid were measured, the viscosity was 4.9 mPa · s, the surface tension was 24.3 mN / m, and the pH was 1.5.

<Composition of treatment liquid T-1>
・ Citric acid (Wako Pure Chemical Industries, Ltd.) ... 16.7% by mass
・ Diethylene glycol monomethyl ether (Wako Pure Chemical Industries, Ltd.) ... 20.0% by mass
・ Zonyl FSN-100 (manufactured by DuPont) ... 1.0% by mass
・ Ion-exchanged water ... 62.3 mass%

  The surface tension is measured using Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) at 25 ° C, and the viscosity is measured by VISCOMETER TV-22 (manufactured by TOKI SANGYO CO.LTD). ) Under the conditions of 20 ° C. The pH was measured at 25 ° C.

<Preparation of water-based ink>
(Synthesis of polymer dispersant P-1)
According to the following scheme, a polymer dispersant P-1 was synthesized as shown below.

To a 1000 ml three-necked flask equipped with a stirrer and a condenser, 88 g of methyl ethyl ketone was added and heated to 72 ° C. in a nitrogen atmosphere. Then, a solution in which 10 g of methacrylic acid and 30 g of methyl methacrylate were dissolved was dropped over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour, and then a solution of 0.42 g of dimethyl 2,2′-azobisisobutyrate in 2 g of methyl ethyl ketone was added, heated to 78 ° C. and heated for 4 hours. The obtained reaction solution was reprecipitated twice in a large excess amount of hexane, and the precipitated resin was dried to obtain 96 g of a polymer dispersant P-1.
The composition of the obtained resin was confirmed by ¹ H-NMR, and the weight average molecular weight (Mw) determined by GPC was 44,600. Furthermore, when the acid value was calculated | required by the method as described in JIS specification (JISK0070: 1992), it was 65.2 mgKOH / g.

(Preparation of dispersion of resin-coated pigment particles)
Pigment Blue 15: 3 (phthalocyanine bull-A220, manufactured by Dainichi Seika Co., Ltd.), 5 parts of the polymer dispersant P-1, 42 parts of methyl ethyl ketone, 5.5 parts of 1N NaOH aqueous solution, 87.2 parts of ion-exchanged water was mixed and dispersed with a bead mill using 0.1 mmφ zirconia beads for 2 to 6 hours.
After removing methyl ethyl ketone at 55 ° C. under reduced pressure and removing a part of water in the obtained dispersion, using a high-speed centrifugal cooler 7550 (manufactured by Kubota Seisakusho), using a 50 mL centrifuge, Centrifugation was performed at 8000 rpm for 30 minutes, and the supernatant liquid other than the precipitate was collected. Thereafter, the pigment concentration was determined from the absorbance spectrum, and a dispersion of resin-coated pigment particles having a pigment concentration of 10.2% by mass was obtained.

(Synthesis of self-dispersing polymer particles)
360.0 g of methyl ethyl ketone was charged into a 2-liter three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, and the temperature was raised to 75 ° C. Thereafter, while maintaining the temperature in the flask at 75 ° C., 180.0 g of phenoxyethyl acrylate, 162.0 g of methyl methacrylate, 18.0 g of acrylic acid, 72 g of methyl ethyl ketone, and “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) 1 .44 g of the mixed solution was added dropwise at a constant speed so that the addition was completed in 2 hours. After completion of the dropwise addition, a solution composed of 0.72 g of “V-601” and 36.0 g of methyl ethyl ketone was added thereto, stirred at 75 ° C. for 2 hours, and further a solution composed of 0.72 g of “V-601” and 36.0 g of isopropanol. And stirred at 75 ° C. for 2 hours. Thereafter, the temperature was raised to 85 ° C., and stirring was further continued for 2 hours to obtain a resin solution of a phenoxyethyl acrylate / methyl methacrylate / acrylic acid (= 50/45/5 [mass ratio]) copolymer.
The weight average molecular weight (Mw) of the obtained copolymer was 64,000 (calculated in terms of polystyrene by gel permeation chromatography (GPC)), and the acid value was 38.9 (mgKOH / g).

  Next, 668.3 g of the obtained resin solution was weighed, 388.3 g of isopropanol and 145.7 ml of 1 mol / L NaOH aqueous solution were added thereto, and the temperature in the reaction vessel was raised to 80 ° C. Next, 720.1 g of distilled water was added dropwise at a rate of 20 ml / min to disperse in water, and then the reaction vessel internal temperature was 80 ° C. for 2 hours, 85 ° C. for 2 hours, and 90 ° C. for 2 hours under atmospheric pressure. After maintaining, the inside of the reaction vessel is evacuated, and 913.7 g of isopropanol, methyl ethyl ketone, and distilled water are distilled off in total to obtain an aqueous dispersion of self-dispersing polymer fine particles B-1 having a solid content concentration of 28.0% by mass. It was.

(Preparation of water-based ink)
Using the dispersion of resin-coated pigment particles obtained above, each component was mixed so as to have the following compositions to prepare cyan and magenta pigment ink liquids. After the liquid preparation, each of the obtained pigment ink liquids was packed in a plastic disposable syringe and filtered through a PVDF 5 μm filter (Millex-SV, diameter 25 mm, manufactured by Millipore) to prepare cyan ink and magenta ink. Moreover, the viscosity, surface tension, and pH measured by the method similar to the above are shown.

<Cyan ink C-1>
・ Cyan pigment (Pigment Blue 15: 3): 4% by mass
-Said polymer dispersing agent P-1 ... 2 mass%
・ Diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 10% by mass
・ Glycerin (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 20% by mass
・ Orphine E1010 (manufactured by Nissin Chemical Co., Ltd., surfactant): 1% by mass
・ Ion-exchanged water: 63% by mass
[Physical properties of cyan ink C-1]
Viscosity: 3.3 mPa · s, surface tension: 32.8 mN / m

<Cyan ink C-10> (for comparison)
・ Cyan pigment (Pigment Blue 15: 3): 4% by mass
-Said polymer dispersing agent P-1 ... 2 mass%
-Self-dispersing polymer fine particle B-1 ... 8 mass% (solid content)
・ Diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 10% by mass
・ Glycerin (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 20% by mass
・ Orphine E1010 (manufactured by Nissin Chemical Co., Ltd., surfactant): 1% by mass
・ Ion exchange water: 63%
[Physical properties of cyan ink C-10]
Viscosity: 5.8 mPa · s, surface tension: 34.9 mN / m

<Cyan ink C-11> (for comparison)
・ Cyan pigment (Pigment Blue 15: 3): 4% by mass
-Said polymer dispersing agent P-1 ... 2 mass%
・ Jonkrill 537 (manufactured by BASF Japan, polymer particles) ... 8% by mass (solid content)
・ Diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 10% by mass
・ Glycerin (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 20% by mass
・ Orphine E1010 (manufactured by Nissin Chemical Co., Ltd., surfactant): 1% by mass
・ Ion-exchanged water: 63% by mass
[Physical properties of cyan ink C-11]
Viscosity: 5.9 mPa · s, surface tension: 35.0 mN / m

<Magenta ink M-1>
・ Magenta pigment (Pigment Red 122): 4% by mass
-Said polymer dispersing agent P-1 ... 2 mass%
・ Diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 10% by mass
・ Glycerin (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 20% by mass
・ Orphine E1010 (manufactured by Nissin Chemical Co., Ltd., surfactant): 1% by mass
・ Ion-exchanged water: 63% by mass
[Physical properties of magenta ink M-1]
Viscosity: 3.6 mPa · s, surface tension: 33.3 mN / m

<Magenta ink M-10> (for comparison)
・ Magenta pigment (Pigment Red 122): 4% by mass
-Said polymer dispersing agent P-1 ... 2 mass%
-Self-dispersing polymer fine particle B-1 ... 8 mass% (solid content)
・ Diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 10% by mass
・ Glycerin (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 20% by mass
・ Orphine E1010 (manufactured by Nissin Chemical Co., Ltd., surfactant): 1% by mass
[Physical properties of magenta ink M-10]
Viscosity: 6.0 mPa · s, surface tension: 35.0 mN / m

<Magenta ink M-11> (for comparison)
・ Magenta pigment (Pigment Red 122): 4% by mass
-Said polymer dispersing agent P-1 ... 2 mass%
・ Jonkrill 537 (manufactured by BASF Japan, polymer particles) ... 8% by mass (solid content)
・ Diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 10% by mass
・ Glycerin (manufactured by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent): 20% by mass
・ Orphine E1010 (manufactured by Nissin Chemical Co., Ltd., surfactant): 1% by mass
・ Ion-exchanged water: 63% by mass

<Preparation of second treatment liquid>
(Processing liquid V-1)
The component of the following composition was mixed and the process liquid V-1 (2nd process liquid) was prepared.
<Composition>
-Self-dispersing polymer fine particles B-1 ... 8% by mass
・ Sanix GP250 (manufactured by Sanyo Chemical Industries, Ltd., hydrophilic organic solvent): 10% by mass
・ Diethylene glycol monoethyl ether: 5% by mass
・ Orphine E1010 (manufactured by Nissin Chemical Co., surfactant): 1% by mass
・ Ion exchange water: 76% by mass

(Processing liquid V-2)
In the treatment liquid V-1, the treatment liquid V-1 was prepared in the same manner as in the preparation of the treatment liquid V-1, except that the self-dispersing polymer fine particles B-1 in the composition were replaced with the following self-dispersing polymer fine particles B-2. V-2 was prepared.

-Synthesis of self-dispersing polymer fine particles B-2-
In the synthesis of the aqueous dispersion of the self-dispersing polymer particles B-1, synthesis was performed in the same manner as the aqueous dispersion of the self-dispersing polymer particles B-1, except that the composition ratio of the monomers was changed. An ethyl acrylate / methyl methacrylate / acrylic acid (= 53/42/5 [mass ratio]) copolymer was obtained.
When the weight average molecular weight (Mw) and the acid value were measured in the same manner as described above, the weight average molecular weight was 69,000 (calculated in terms of polystyrene by gel permeation chromatography (GPC)), and the acid value was 38.9 mgKOH. / G.

<Image recording and evaluation 1>
-1. Image quality (color material movement)
First, as a recording medium, Tokuhishi art double-sided N (water absorption coefficient Ka = 0.21 mL / m ² · ms ^1/2 ; manufactured by Mitsubishi Paper Industries Co., Ltd.) was prepared and obtained from the above as shown below. The applied treatment liquid T-1 (first treatment liquid) was applied and dried, and then images were recorded using cyan ink, magenta ink, and treatment liquids V-1 to V-2 (second treatment liquid). For recording, a GELJET GX5000 printer head (full line head manufactured by Ricoh) was prepared as a recording head, and the cyan and magenta inks obtained above and the processing liquids V-1 and V- Refilled to 2.

First, the Tokuhishi art both sides N are fixed on a stage that can move linearly in a predetermined direction at 500 mm / second, and the treatment liquid T-1 (first treatment liquid) obtained above is fixed to this with a wire bar coater. The film was applied to a thickness of 5 μm (citric acid 0.84 g / m ² ), and was dried at 50 ° C. for 2 seconds immediately after the application. Thereafter, the GELJET GX5000 printer head (full line head manufactured by Ricoh) has a line head direction (main scanning direction) of 75. with respect to a direction orthogonal to the stage moving direction (sub scanning direction). The ink is fixedly arranged so as to incline by 7 °, and cyan ink is ejected in a line system under the ejection conditions of an ink droplet amount of 3.5 pL, an ejection frequency of 24 kHz, and a resolution of 1200 dpi × 600 dpi while moving the recording medium at a constant speed in the sub-scanning direction. The ink was discharged, and a cyan solid image was printed. Subsequently, magenta ink was ejected so as to overlap the cyan solid image, and a magenta solid image was printed. At this time, the interval from the end of cyan ink droplet ejection to the start of magenta ink droplet ejection was set to 50 milliseconds. The combinations of cyan ink and magenta ink are shown in Table 1 below. Next, after printing a solid image of magenta color, the processing liquid V-1 or the processing liquid V-2 (second processing liquid) was further discharged by a line method under the same discharge conditions as described above.
Immediately after discharging the second processing liquid, it is dried at 60 ° C. for 3 seconds, further passed between a pair of fixing rollers heated to 60 ° C., and subjected to a fixing process with a nip pressure of 0.25 MPa and a nip width of 4 mm, and evaluation A sample was obtained. The fixing roller is composed of a heating roll in which the surface of the core of a SUS cylindrical body with a halogen lamp inside is coated with a silicone resin, and an opposing roll that is in pressure contact with the heating roller. is there.
The evaluation of the image quality (coloring material movement) was performed according to the following evaluation criteria based on the limit sample shown in FIG. 2 by visually observing the evaluation sample obtained as described above. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: As shown in the sample (A), no color material movement was observed.
(Triangle | delta): As shown to a sample (B), color material movement was slight.
X: As shown in the sample (C), color material movement occurred.

-2. Fixing (Abrasion resistance)-
The unprinted special diamond art cut to 10 mm × 50 mm is wrapped around a paperweight (weight 470 g, size 15 mm × 30 mm × 120 mm) (the area where the unprinted special diamond art and the evaluation sample are in contact is 150 mm ² ). The evaluation sample created in the evaluation of “.Image quality (coloring material movement)” was rubbed 3 times (corresponding to a load of 260 kg / m ² ). The printed surface after rubbing was visually observed and evaluated according to the following evaluation criteria.
<Evaluation criteria>
◯: The peeling of the image (color material) on the printed surface was not visually recognized.
X: The peeling of the image (color material) of the printing surface was visually recognizable.

  As shown in Table 1, no. 4-No. In No. 5 (invention), when a two-color image was formed, color material movement was suppressed, and a multicolor image having good color density and hue and excellent scratch resistance was obtained. On the other hand, no. 1 and no. From No. 2 (Comparative Example), when polymer particles are contained in the water-based ink, color material movement occurs when an image of the second color is recorded, and an image free from density unevenness and color unevenness cannot be obtained. It was. No. From the result of No. 3, when polymer particles are contained in the water-based ink, the movement of the coloring material is not suppressed even when the second treatment liquid is applied, and the fixing property is also lowered.

<Evaluation 2>
Furthermore, the effect on the recorded image due to the presence or absence of the first treatment liquid was evaluated using the offset property as an index.
-3. Offset −
In the same manner as in the evaluation of “1. Image quality (coloring material movement)”, the presence or absence of occurrence of offset at the time of heat and pressure fixing when an evaluation sample was prepared was visually observed and evaluated according to the following evaluation criteria.
<Evaluation criteria>
○: The color material of the solid image adhered to the fixing roller.
X: Adhesion of the color material of the solid image to the fixing roller was not observed.

  As shown in Table 2 above, no. 11 and No. From the comparison with No. 12, it was found that in the system not using the first treatment liquid, offset occurs during fixing.

It is a schematic block diagram which shows the structural example of the inkjet recording device used for implementation of the image recording method of this invention. A limit sample for evaluating image quality (color material movement) is shown, (A) is a sample showing a state in which no color material movement is observed, and (B) is a state in which color material movement has occurred slightly. (C) is a sample representing a state in which color material movement has occurred.

Explanation of symbols

DESCRIPTION OF SYMBOLS 12 ... 1st process liquid provision part 12S ... 1st process liquid discharge head 13 ... Process liquid drying zone 14 ... Ink discharge part 15 ... Ink drying zone 16 ... Image fixing part 30C, 30M, 30Y, 30K... Ink ejection head 30A... Second treatment liquid ejection head

Claims (13)

A water-based ink composition containing a water-insoluble colorant, a hydrophilic organic solvent, a surfactant, and water, and the content of polymer particles is 6% by mass or less of solids;
A first treatment liquid capable of forming an aggregate when contacted with the aqueous ink composition;
A second treatment liquid containing polymer particles, a hydrophilic organic solvent, a surfactant, and water, and a colorant content of 0.1% by mass or less;
An ink set for ink-jet recording comprising:   2. The ink set for ink jet recording according to claim 1, wherein the polymer particles in the second treatment liquid are self-dispersing polymer particles.   The polymer particles in the second treatment liquid are synthesized in an organic solvent, neutralized part or all of anionic groups, and prepared as a polymer dispersion having water as a continuous phase. The ink set for inkjet recording according to claim 1 or 2, wherein the ink set is used for ink jet recording.   The ink set for inkjet recording according to any one of claims 1 to 3, wherein the polymer particles in the second treatment liquid are acrylic resin particles.   The ink set for inkjet recording according to any one of claims 1 to 4, wherein the water-insoluble colorant in the water-based ink composition is a pigment coated with a polymer dispersant.   The ink set for ink jet recording according to claim 5, wherein the polymer dispersant is an acrylic polymer.   The ink set for inkjet recording according to any one of claims 1 to 6, wherein the first treatment liquid contains a compound having a carboxyl group or a salt thereof. Ink that contains a water-insoluble colorant, a hydrophilic organic solvent, a surfactant, and water, and an aqueous ink composition having a polymer particle content of 6% by mass or less on a recording medium by an inkjet method. Granting process;
A first treatment liquid applying step of applying a first treatment liquid capable of forming an aggregate on the recording medium when contacted with the aqueous ink composition;
A second treatment liquid applying step of applying a second treatment liquid containing polymer particles, a hydrophilic organic solvent, a surfactant, and water and having a coloring material content of 0.1% by mass or less onto the recording medium; ,
An ink jet recording method comprising:   On the recording medium, after applying the first treatment liquid in the first treatment liquid application step, the ink application step is provided to apply the aqueous ink composition, and on at least the applied aqueous ink composition, The inkjet recording method according to claim 8, wherein the second treatment liquid is applied in the second treatment liquid application step. Having the ink application step after the first treatment liquid application step;
A heating drying step of heating and drying the first processing liquid on the recording medium after applying the first processing liquid on the recording medium and before applying the aqueous ink composition is provided. The ink jet recording method according to claim 8 or 9.   11. The ink jet recording method according to claim 8, wherein the ink application step applies the water-based ink composition by a line method. The inkjet recording according to any one of claims 8 to 11, wherein the recording medium has a water absorption coefficient Ka of 0.05 to 0.5 mL / m ² · ms ^1/2. Method.   A recorded matter recorded by the ink jet recording method according to any one of claims 8 to 12.