JP2009125958A - RECORDING MEDIUM, MANUFACTURING METHOD THEREOF, AND INK JET RECORDING METHOD - Google Patents

Abstract

A recording medium capable of forming a high-quality image close to offset printing at low cost and at high speed, a manufacturing method thereof, and an inkjet recording method are provided.
A first layer containing a crosslinking agent and a binder capable of forming a covalent bond between a base paper and a compound having an amino group, a white pigment, and a compound having two or more amino groups in the molecule. The surface of the first layer of the base paper provided with the first layer has a Cobb water absorbency of 2 at a contact time of 120 seconds according to a water absorbency test according to JIS P8140. a is .0g / ^{m 2} or less, which is the second layer recording medium water absorption amount at a contact time of 0.5 sec is 2 mL / ^{m 2} or more 8 mL / ^{m 2} or less determined by a Bristow test at a surface of the.
[Selection figure] None

Description

  The present invention relates to a recording medium, a manufacturing method thereof, and an ink jet recording method using the same.

  The ink jet apparatus has a simple structure, and high-quality image recording is possible by ink jet recording performed using the ink jet apparatus. Ink used for inkjet recording is designed to have a surface tension of about 20 mN / m to 40 mN / m, adjusted to a viscosity of about several mPa · s to about 30 mPa · s so that it can be ejected from an inkjet head. .

  In general, the ink contains 50% to 90% of an ink solvent so that the viscosity of the ink falls within the above range. As the ink solvent, water, an organic solvent, oil, a photopolymerizable monomer, and the like are used, and water is often used particularly from the viewpoint of environmental suitability. Further, a high boiling point solvent such as glycerin is generally used as the ink solvent so that the discharge nozzle of the ink jet head does not cause clogging due to drying of the ink solvent.

  On the other hand, when a large amount of ink solvent is present in the ink-drawn recording medium, image bleeding and color mixing between colors are likely to occur due to the large amount of ink solvent. For this reason, an ink jet dedicated paper (see FIG. 5) having a solvent absorbing layer (ink receiving layer) of about 20 to 30 μm for absorbing the ink solvent is used as a recording medium, and image bleeding and color mixing between colors occur. Is suppressed.

  Further, in the case of water-based ink using water as an ink solvent, paper permeation such as curling occurs when water penetrates into the base paper during recording. However, as shown in FIG. When the solvent absorption layer 22 is provided on the top, water can be prevented from penetrating into the base paper, and paper deformation can be suppressed.

  In particular, when a graphical image with a high image density or image area ratio is to be formed, the amount of ink per unit area on the recording medium increases, and the solvent absorption layer cannot suppress the penetration of the ink solvent into the base paper. Therefore, water-resistant paper (for example, laminated paper) covered with a resin layer using polyolefin or the like is generally used (see, for example, Patent Documents 1 and 2).

  However, the ink jet technology is not only applied in the fields of office printers, home printers, etc., but has recently been applied in the field of commercial printing. This commercial printing field does not have a photo-like surface that completely shuts out the penetration of the ink solvent into the base paper, but requires a printing texture like general-purpose printing paper. Therefore, when the solvent absorption layer constituting the recording medium is as thick as 20 to 30 μm, the surface gloss, texture, stiffness, etc. of the recording medium are limited. However, it is limited to posters, form printing, and the like that are allowed to be limited in terms of surface gloss, texture, stiffness, etc., on the recording medium.

  Further, the recording medium has a high cost due to the solvent absorption layer and the water resistant layer, which also contributes to the above limitation.

As a technique related to the above, a coating liquid for offset printing paper in which a fatty acid / polyalkylene polyamine condensate and an epoxy resin emulsion are used in combination is disclosed (for example, see Patent Document 3), and water resistance is improved. ing. In addition, an ink jet recording medium having a glossy expression layer containing a water-soluble resin having a carbodiimide group and a water-soluble resin having a carboxyl group, a hydroxyl group, and an amino group has been disclosed (for example, see Patent Document 4). Furthermore, as a coating composition that imparts excellent ink acceptability and water resistance to paper, an amine compound (I) comprising an aliphatic amine and a glycidyl compound, an epihalohydrin and / or a polyvalent carboxylic acid, an aliphatic amine, and urea There is a disclosure relating to a resin composition for paper coating in which an amine compound (II) which is a reactive organism is mixed (see, for example, Patent Document 5).
JP 2005-238829 A JP 2005-96285 A JP-A-7-229092 JP 2006-231648 A JP 2006-160896 A

  However, in any of the coating liquids and compositions described in the above-mentioned patent documents, a high level of water resistance that can avoid paper deformation such as curling is obtained when a large amount of ink solvent is applied. Absent. In addition, for example, the above-mentioned offset printing paper coating solution and the like, an amine compound such as a fatty acid / polyalkylene polyamine condensate and a compound that is crosslinkable with an amine such as an epoxy resin are mixed to increase the viscosity. Although it is easy to cause and water resistance is obtained, a good surface condition cannot be obtained due to cracks and the like.

  The present invention has been made in view of the above, and a recording medium having good liquid resistance and recording surface properties, curling accompanying image recording, image bleeding, and color mixing between colors, and its recording medium PROBLEM TO BE SOLVED: To provide a manufacturing method and an ink jet recording method capable of forming a high quality image close to offset printing at a low cost and at a low cost by preventing occurrence of curling, image bleeding and color mixing between the images. The purpose is to achieve the purpose.

Specific means for achieving the above object are as follows.
<1> A first layer containing a crosslinking agent and a binder capable of forming a covalent bond between a base paper and a compound having an amino group, a white pigment and a first layer containing a compound having two or more amino groups in the molecule The surface of the first layer of the base paper on which the first layer is provided has a Cobb water absorption of 2 for a contact time of 120 seconds according to a water absorption test according to JIS P8140. a is .0g / ^{m 2} or less, which is the second layer recording medium water absorption amount at a contact time of 0.5 sec is 2 mL / ^{m 2} or more 8 mL / ^{m 2} or less determined by a Bristow test at a surface of the.
<2> The compound having two or more amino groups in the molecule in the second layer is at least one selected from the group consisting of a polyalkylene polyamine, an alkylamine / epihalohydrin, and gelatin. The recording medium according to <1>.
<3> The cross-linking agent in the first layer is at least one selected from the group consisting of an epoxy compound, a compound having an active methylene group, cyanuric chloride, a formaldehyde precursor, and a carbodiimide. <1> or the recording medium according to <2>.

<4> The recording medium according to any one of <1> to <3>, wherein the binder in the first layer includes a thermoplastic resin.
<5> The recording medium according to <4>, wherein the thermoplastic resin is at least one selected from polyester urethane latex and acrylic silicone latex.
<6> The recording medium according to any one of <1> to <5>, wherein the first layer further includes a white pigment.
<7> The recording medium according to any one of <1> to <6>, wherein the white pigment is kaolin.

<8> On the base paper, a film-forming liquid containing a crosslinking agent capable of forming a covalent bond with a compound having an amino group and thermoplastic resin particles is applied, and the temperature is equal to or higher than the minimum film-forming temperature of the thermoplastic resin particles. A first forming step of forming a first layer by heat treatment in a temperature region; and a film forming liquid containing a white pigment and a compound having two or more amino groups in the molecule on the first layer. And a second forming step of forming a second layer by applying, and manufacturing the recording medium according to any one of <4> to <7>. .
<9> The method for producing a recording medium according to <8>, wherein the thermoplastic resin particles are at least one selected from polyester urethane latex and acrylic silicone latex.

<10> An ink drawing process in which ink is applied to the recording medium according to any one of <1> to <7> and ink is drawn according to predetermined image data, and the recording medium on which ink is drawn And a drying removal step of drying and removing the ink solvent.
<11> A treatment liquid supply step for supplying a treatment liquid containing an acidic substance to the recording medium according to any one of <1> to <7>, and an ink for the recording medium to which the treatment liquid is supplied. And an ink drawing process for drawing ink according to predetermined image data, and a drying removal process for drying and removing the ink solvent in the recording medium on which ink has been drawn.

According to the present invention, it is possible to provide a recording medium that has good liquid resistance and surface properties of the recording surface, prevents curling accompanying image recording, and prevents image bleeding and color mixing between colors, and a method for manufacturing the same. it can. This makes it possible to form a high-quality image close to offset printing at a low cost and at a high speed. Also,
According to the present invention, there is provided an inkjet recording method capable of preventing the occurrence of curling, image bleeding, and color mixing between colors, and forming a high-quality image close to offset printing at low cost and at high speed. be able to.

  Hereinafter, the recording medium of the present invention, the manufacturing method thereof, and the ink jet recording method using the recording medium will be described in detail.

<Recording medium>
The recording medium of the present invention comprises a base paper and a first layer and a second layer provided in this order from the base paper side, and if necessary, further appropriately selected other layers are provided. Can be configured. The recording medium of the present invention includes, for example, a high-quality paper 11 as a base paper, a solvent blocking layer 12 as a first layer formed on the high-quality paper 11, and a solvent, like a recording medium 100 shown in FIG. A coating layer 13 as a second layer formed on the blocking layer 12 is provided. The recording medium may be either sheet paper or roll paper.

(Base paper)
There is no restriction | limiting in particular as a base paper, According to the objective, it can select suitably from well-known things.

  The pulp that can be used as the raw material of the base paper is preferably hardwood bleached kraft pulp (LBKP) from the viewpoint of improving the surface smoothness, rigidity and dimensional stability (curlability) of the base paper to a balanced and high level at the same time. In addition, softwood bleached kraft pulp (NBKP), hardwood sulfite pulp (LBSP), and the like can be used.

  A beater or refiner can be used for beating the pulp. In the pulp slurry obtained after beating the pulp (hereinafter sometimes referred to as “pulp paper material”), various additives such as a filler, a dry paper strength enhancer, a sizing agent, and wet paper strength are used as necessary. An enhancer, a fixing agent, a pH adjuster, other chemicals, and the like are added.

Examples of the filler include calcium carbonate, clay, kaolin, white clay, talc, titanium oxide, diatomaceous earth, barium sulfate, aluminum hydroxide, magnesium hydroxide and the like.
Examples of the dry paper strength enhancer include cationized starch, cationized polyacrylamide, anionized polyacrylamide, amphoteric polyacrylamide, and carboxy-modified polyvinyl alcohol.
Examples of the sizing agent include rosin derivatives such as fatty acid salts, rosin and maleated rosin, paraffin wax, alkyl ketene dimer, alkenyl succinic anhydride (ASA), and epoxidized fatty acid amide.
Examples of the wet paper strength enhancer include polyamine polyamide epichlorohydrin, melamine resin, urea resin, and epoxidized polyamide resin.
Examples of the fixing agent include polyvalent metal salts such as aluminum sulfate and aluminum chloride, and cationic polymers such as cationized starch.
Examples of the pH adjuster include caustic soda and sodium carbonate.
Examples of other chemicals include antifoaming agents, dyes, slime control agents, fluorescent whitening agents, and the like.

  Moreover, a softening agent etc. can also be added to a pulp paper stock as needed. The softening agent is described in, for example, New Paper Processing Handbook (edited by Paper Medicine Time), pages 554 to 555 (issued in 1980).

The treatment liquid used for the surface sizing treatment may contain, for example, a water-soluble polymer, a sizing agent, a water-resistant substance, a pigment, a pH adjusting agent, a dye, and a fluorescent brightening agent.
Examples of the water-soluble polymer include cationized starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose sulfate, gelatin, casein, sodium polyacrylate, styrene-maleic anhydride copolymer sodium salt, Examples thereof include sodium polystyrene sulfonate.
Examples of the sizing agent include petroleum resin emulsion, ammonium salt of styrene-maleic anhydride copolymer alkyl ester, rosin, higher fatty acid salt, alkyl ketene dimer (AKD), epoxidized fatty acid amide and the like.
Examples of the water-resistant substance include latex / emulsions such as styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, polyethylene, vinylidene chloride copolymer, polyamide polyamine epichlorohydrin, and the like.
Examples of the pigment include calcium carbonate, clay, kaolin, talc, barium sulfate, and titanium oxide.
Examples of the pH adjuster include hydrochloric acid, caustic soda, sodium carbonate, and the like.

  Examples of the material of the base paper include synthetic pulp paper, mixed paper of natural pulp and synthetic pulp, and various types of combined paper, in addition to the above-described natural pulp paper.

  As thickness of a base paper, 30-500 micrometers is preferable, More preferably, it is 50-300 micrometers, More preferably, it is 70-200 micrometers.

(First layer)
The recording medium of the present invention has a first layer on the base paper. By providing the first layer, the penetration of the ink solvent into the base paper is suppressed. For example, as a paper provided with a solvent blocking layer, a paper having a coating layer mainly composed of polyethylene resin on the surface of the base paper is known. However, with the paper provided with the above-described solvent blocking layer to give water resistance, the water penetration preventing effect can be obtained almost completely, but the paper texture is not always satisfactory.
The first layer includes at least a cross-linking agent capable of forming a covalent bond with a compound having an amino group, and a binder, and JIS on the surface of the first layer of the base paper provided with the first layer. The Cobb water absorption for a contact time of 120 seconds according to the water absorption test in accordance with P8140 is set to 2.0 g / m ² or less. If it is this range, there will be no restriction | limiting in particular, As a 1st layer, it can select suitably from well-known things according to the objective.
Moreover, a 1st layer can be comprised using other components, such as a white pigment, as needed other than the said crosslinking agent and a binder.

  The first layer in the present invention is, for example, a thermoplastic resin (preferably latex, more preferably polyester urethane latex, acrylic silicone latex) as a binder in terms of suppressing penetration of the ink solvent and obtaining good surface properties. A layer in which kaolin is used as a white pigment and the mass ratio x / y of the mass (solid content) x of the thermoplastic resin to the mass y of the kaolin is 1 to 30, and further, an epoxy compound, an active methylene group A layer using a cross-linking agent selected from a compound having a cyanuric chloride, a formaldehyde precursor, and a carbodiimide is preferable.

-Binder-
The first layer contains at least one binder. The binder is used for the purpose of improving not only the dispersion but also the coating film strength.
Examples of the binder include polyvinyl alcohol (including modified polyvinyl alcohols such as acetoacetyl modification, carboxy modification, itaconic acid modification, maleic acid modification, silica modification and amino group modification), methylcellulose, carboxymethylcellulose, starches (modified starch). ), Gelatin, arabic gum, casein, styrene-maleic anhydride copolymer hydrolyzate, polyacrylamide, saponified vinyl acetate-polyacrylic acid copolymer, and the like. Examples thereof also include latex binders of synthetic polymers such as styrene / butadiene copolymer, vinyl acetate copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, and polyvinylidene chloride.

  The polyvinyl alcohol includes polyvinyl alcohol obtained by saponifying a lower alcohol solution of polyvinyl acetate and derivatives thereof, and a saponified product of a copolymer of a monomer and vinyl acetate that can be copolymerized with vinyl acetate. It is. Here, as monomers that can be copolymerized with vinyl acetate, (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid and other unsaturated carboxylic acids and esters thereof, ethylene, propylene, etc. Α-olefin, olefin sulfonic acid such as (meth) allyl sulfonic acid, ethylene sulfonic acid, sulfonic acid malate, (meth) allyl sulfonic acid soda, ethylene sulfonic acid soda, sulfonic acid soda (meth) acrylate, sulfonic acid soda ( Monoalkylmalates), olefinic sulfonic acid alkali salts such as sodium disulfonic acid alkylmalate, amide group-containing monomers such as N-methylolacrylamide, alkali acrylamide alkylsulfonic acid salts, and N-vinylpyrrolidone derivatives Can be mentioned.

  Of the polyvinyl alcohols, acetoacetyl-modified polyvinyl alcohol can be generally produced by adding and reacting a liquid or gaseous diketene to the solution, dispersion or powder of the polyvinyl alcohol resin. The acetylation degree of acetoacetyl-modified polyvinyl alcohol can be appropriately selected according to the intended quality, but is preferably 0.1 mol% to 20 mol%, more preferably 0.5 mol% to 10 mol%. It is.

  As the binder, polyolefins such as α-olefin homopolymers such as polyethylene, polypropylene and polyvinyl chloride or mixtures thereof; polyamides and polyimides; polyesters such as polyethylene terephthalate; and other general-purpose thermoplastic polymers , Α-methylene fats such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, etc. Styrenes such as styrene, chlorostyrene and vinyl styrene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate; vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether, etc. Vinyl ether Homopolymers of vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropenyl ketone, etc., or arbitrary copolymers containing these structural units, and the like of known thermoplastic resins and their latexes. It can be suitably selected from the inside.

Among these, a thermoplastic resin is preferable and latex is more preferable in terms of water blocking properties. Latex includes acrylic latex, acrylic silicone latex, acrylic epoxy latex, acrylic styrene latex, acrylic urethane latex, styrene-butadiene latex, acrylonitrile-butadiene latex, polyester urethane latex, and vinyl acetate latex. And the like.
In particular, polyester-based urethane latex and acrylic silicone-based latex are preferable because they have high ink solvent permeability and cockling-suppressing effects and have both economic efficiency and production suitability.

  The molecular weight of the latex is preferably 3,000 to 1,000,000 in terms of number average molecular weight, and more preferably about 5,000 to 100,000. When the molecular weight is 3,000 or more, the mechanical strength of the first layer can be secured, and when it is 1,000,000 or less, it is advantageous in terms of production suitability such as dispersion stability and viscosity.

Specifically, as the acrylic latex, a commercially available product can be used. For example, the following water-dispersible latex can be used. That is, examples of acrylic resins include “Cebian A4635, 46583, 4601” manufactured by Daicel Chemical Industries, Ltd., “Nipol Lx811, 814, 821, 820, 857” manufactured by Nippon Zeon Co., Ltd. . In particular, acrylic emulsions of acrylic silicon latex described in JP-A-10-264511, JP-A-2000-43409, JP-A-2000-343811, and JP-A-2002-120452 (commercially available products include, for example, Daicel Aquabrid series UM7760, UM7611, UM4901, Aquabrid 903, Asi-86, ASi-89, Asi-91, ASi-753, 4635, 4901, MSi-04S, Chemical Industries, Ltd. AU-124, AU-131, AEA-61, AEC-69, AEC-162, etc.) can also be suitably used.
Examples of the polyester-based urethane latex include, as commercial products, HYDRAN AP series (for example, HYDRAN AP-20, AP-30, AP-30F, and AP-40 manufactured by Dainippon Ink & Chemicals, Inc.). (F), the same AP-50LM, the same APX-101H, the same APX-110, the same APX-501, etc.).
In addition, it is preferable to select and use at least one of the above thermoplastic resins from the above, and it may be used alone or in combination of two or more.

  The glass transition temperature (Tg) of the thermoplastic resin is preferably 5 to 70 ° C, and particularly preferably 15 to 50 ° C. When the Tg is particularly within the above range, problems such as burrs of the film forming liquid for forming the first layer (for example, coating liquid) are prevented, and handling in manufacturing is easy, and Tg is high. If the calendar temperature is not set too high, the desired gloss cannot be obtained, and adhesion to the metal roll surface is likely to occur. High planarity can be obtained.

  The minimum film-forming temperature of the thermoplastic resin (preferably latex resin fine particles) is preferably 20 to 60 ° C, and more preferably 25 to 50 ° C. When the minimum film forming temperature range where film formation is possible when trying to form a film is particularly within the above range, problems such as burrs of the film forming liquid for forming the first layer (for example, coating liquid) can be prevented. It is easy to handle in production, and the penetration when the second layer is formed is suppressed, the coated surface of the second layer to be formed is good, and the ink solvent can be quickly transmitted. A layer having sufficient microporosity can be formed. Although a layer only provided with a liquid (for example, a coating solution) does not necessarily have good glossiness, a high glossiness layer having microporosity can be obtained by performing a soft calender treatment later.

  As content in the 1st layer of a binder (preferably thermoplastic resin), 15-95 mass% is preferable with respect to the total solid of this 1st layer, and 30-90 mass% is more preferable. When the content is particularly within the above range, gloss and flatness are good when calendar treatment is performed, ink solvent permeability is obtained, and the occurrence of bleeding with time is more effectively prevented. Can do.

  Moreover, you may add the crosslinking agent of a suitable binder to a 1st layer according to the kind of these binder as needed.

-Crosslinking agent-
The first layer contains at least one crosslinking agent capable of forming a covalent bond with the compound having an amino group. This cross-linking agent forms a covalent bond with a compound having two or more amino groups in a molecule contained in a second layer described later provided as an upper layer of the first layer on the base paper, thereby Water resistance is improved, and a good surface shape in which occurrence of cracks and the like is suppressed is obtained.

  As a crosslinking agent capable of forming a covalent bond with a compound having an amino group, an epoxy compound, a compound having an active methylene group, cyanuric chloride (2,4,6-trichloro-1,3,5-triazine), Examples include formaldehyde precursors, polyaldehydes, epihalohydrins, α, ω-dihalo-β-hydrins, polyisocyanate compounds, carbodiimides, vinyl compounds, and the like.

  The epoxy compound is a compound having an epoxy group in the molecule, and a compound having at least two epoxy groups in the molecule is preferable. Specifically, for example, alkylene glycol diglycidyl ethers such as ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether; polyoxyalkylene glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; resorcinol Aromatic polyvalent glycidyl ethers such as diglycidyl ether and bisphenol A diglycidyl ether, vinylcyclohexene dioxide, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate 3- (3,4-epoxycyclohexyl) -8,9-epoxy-2,4-dioxaspiro [5.5] unde Cycloaliphatic diglycidyl compounds such as can, diglycidyl hexahydrophthalate, 2,2-bis (4-glycidyloxycyclohexyl) propane, trimethylolpropane di- or tri-glycidyl ether, sorbitol di-, tri-, tetra- And polyglycidyl ethers of polyhydric alcohols such as penta- or hexa-glycidyl ether, pentaerythritol di-, tri- or tetra-glycidyl ether, and the like.

  Examples of the compound having an active methylene group include 2-ethylenesulfonyl-N- [2- (2-ethylenesulfonyl-acetylamino) -ethyl] -acetamide, bis-2-vinylsulfonylethyl ether, bisacryloylimide, N In addition to —N′-diacryloylurea, 1,1-bisvinylsulfoneethane, ethylene-bis-acrylamide, diacrylate and dimethacrylate compounds represented by the following structural formulas, and the like can be given. Among these, 2-ethylenesulfonyl-N- [2- (2-ethylenesulfonyl-acetylamino) -ethyl] acetamide is particularly preferable.

The formaldehyde precursor is not particularly limited as long as it is a compound having a 2,3-dihydroxy-1,4-dioxane skeleton. For example, 2,3-dihydroxy-5-methyl-1,4-dioxane, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5,6-dimethyl-1,4-dioxane, 2, Examples include 3-dihydroxy-2,5,6-trimethyl-1,4-dioxane, 2,3-dihydroxy-2-methyl-1,4-dioxane and the like.
Examples of the polyaldehyde include alkyl dialdehydes such as glyoxal, propane dial and butane dial.

Epihalohydrin is a compound generally represented by the following general formula (1), and specific examples include epichlorohydrin and epibromohydrin with n = 0.
In the following general formula (1), n represents an integer of 0 to 5, and X represents a halogen atom (for example, chlorine atom, bromine atom, iodine atom, etc.).

α, ω-Dihalo-β-hydrin is a compound generally represented by the following general formula (2), specifically, α, γ-dihalo-β- such as 1,3-dichloro-2-propanol. A hydrin etc. are mentioned.
In the following general formula (2), m represents an integer of 1 to 5, and Y and Z each independently represent a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.).

  Carbodiimide is a compound containing a functional group represented by the chemical formula -N = C = N-, for example, dicyclohexylcarbodiimide, N-N'-diisopropylcarbodiimide, 1-ethyl. -3- (3-dimethylaminopropyl) carbodiimide hydrochloride and the like.

The vinyl compound is not particularly limited as long as it is a compound having two or more vinyl groups in a single molecule. Among these, from the viewpoint of water resistance, a compound having two or more vinyl groups adjacent to a substituent having a positive Hammett's substituent constant σ _p in a single molecule is preferable.

The substituents having a positive Hammett's substituent constant σ _p include CF ₃ group (σ _p value: 0.54), CN group (σ _p value: 0.66), COCH ₃ group (σ _p value: 0). .50), COOH group (σ _p value: 0.45), COOR (R represents an alkyl group) group (σ _p value: 0.45), NO ₂
Group (σ _p value: 0.78), OCOCH ₃ group (σ _p value: 0.31), SH group (σ _p value: 0.
15), SOCH ₃ group (σ _p value: 0.49), SO ₂ CH ₃ group (σ _p value: 0.72), SO ₂ NH ₂ group (σ _p value: 0.57), SCOCH ₃ group ( σ _p value: 0.44), F group (σ _p value: 0.06), Cl group (σ _p value: 0.23), Br group (σ _p value: 0.23), I group (σ _p Value: 0.18), IO ₂ group (σ _p value: 0.76), N ⁺ (CH ₃ ) ₂ group (σ _p value: 0.82), S ⁺ (CH ₃ ) ₂ group (σ _p value) : 0.90) and the like.

  Among the above, from the viewpoint of surface improvement such as water resistance and cracking, one or more selected from the group consisting of an epoxy compound, a compound having an active methylene group, cyanuric chloride, a formaldehyde precursor, and a carbodiimide. It is preferable to use it.

  As content in the 1st layer of the crosslinking agent which can form a covalent bond with the compound which has an amino group, 0.1-30 mass% is with respect to the binder component contained in a 2nd layer. Preferably, 0.5-10 mass% is more preferable. When the content of the cross-linking agent is 0.1 or more, the water resistance of the recording medium is improved, and surface quality deterioration due to cracking or the like is suppressed, and the quality of the recording medium is improved. When it exists, precipitation of a crosslinking agent can be suppressed and planar shape becomes more favorable.

~ Cobb water absorption ~
In the present invention, the Cobb water absorption for a contact time of 120 seconds measured by a water absorption test in accordance with JIS P8140 from the first layer side of the base paper provided with the first layer is 2.0 g / m ² or less. To do. When the Cobb water absorption is 2.0 g / m ² or less, the base paper provided with the first layer has a slow permeability and delays the absorption when a liquid such as ink is applied, thereby generating curls. Can be reduced.
Furthermore, the Cobb water absorption is more preferably 1.0 g / m ² or less. Further, the lower limit value of the Cobb water absorption is preferably 0.2 g / m ² .

  The Cobb water absorption is measured by a water absorption test according to JIS P8140, and water is supplied for a certain period of time from one surface of the base paper, specifically, the surface of the first layer of the base paper provided with the first layer. This is a measure of the amount of water that is absorbed when the water contacts. In the present invention, the contact time is 120 seconds.

In addition to the above components, other components such as a white pigment, a hardener, and a layered inorganic compound can be used for the first layer.
-White pigment-
Examples of white pigments include titanium oxide, barium sulfate, barium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica antimony trioxide, titanium phosphate, aluminum hydroxide, kaolin, clay, talc, magnesium oxide, and hydroxide. And magnesium.
Among the above, titanium oxide is particularly preferable in terms of whiteness, dispersibility, and stability. Further, kaolin is particularly preferable in terms of water blocking. Examples of kaolin include Kaoblite 90 manufactured by Shiroishi Calcium Co., Ltd., kao gloss, kao white, and the like.
Further, when the first layer contains a white pigment, sticking to the calendar can be prevented when the calendar process is performed after the first layer is formed.

  The white pigment preferably contains 75% or more (volume basis) of particles of 2.0 μm or less. When the particle size is within the above range, the whiteness and glossiness become good.

  Titanium oxide may be either a rutile type or an anatase type, and these may be used alone or in combination. Further, any of those manufactured by the sulfuric acid method and those manufactured by the chlorine method may be used. Examples of the titanium oxide include hydrous alumina treatment, hydrous silicon dioxide treatment, or surface coating treatment with an inorganic substance such as zinc oxide treatment, trimethylolmethane, trimethylolethane, trimethylolpropane, and 2,4-dihydroxy-2. -It can select suitably from what carried out surface coating processing by organic substances, such as methylpentane, or siloxane processing, such as polydimethylsiloxane.

The specific surface area of the white pigment by the BET method is preferably less than 100 m ² / g. When a white pigment having a specific surface area in this range is included, the penetration of the coating liquid when the second layer is applied and formed can be suppressed, and the ink absorbability of the second layer can be increased.

  The BET method is one of powder surface area measurement methods by a gas phase adsorption method, and is a method for obtaining a total surface area, that is, a specific surface area of a 1 g sample from an adsorption isotherm. Usually, nitrogen gas is used as the adsorbed gas, and a method of measuring the amount of adsorption from the change in pressure or volume of the gas to be adsorbed is common. A prominent expression of the isotherm of multimolecular adsorption is the Brunauer Emmett, Teller equation (BET equation). Based on this, the amount of adsorption is obtained, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface. .

A white pigment can be used alone or in combination of two or more.
The content of the white pigment in the first layer varies depending on the type of white pigment, the type of thermoplastic resin, the layer thickness, etc., but is usually 5 to 200 mass with respect to the mass (solid content) of the binder. % Is desirable.

-Hardener-
The first layer may include a hardening agent that hardens the binder. The hardener can be appropriately selected depending on the binder. For example, in addition to the compounds mentioned in the section of the crosslinking agent, polyvalent metal salts, boron compounds and the like can be mentioned.

  The content of the hardener in the first layer is preferably 0.1% by mass to 30% by mass, and more preferably 0.5% by mass to 10% by mass with respect to the solid content of the binder. When the content of the hardener is within the above range, the film-forming liquid for forming the first layer does not thicken, and the water resistance of the recording material can be improved.

-Layered inorganic compound-
The first layer may further contain a layered inorganic compound. As the layered inorganic compound, a swellable inorganic layered compound is preferable, for example, swelling viscosity minerals such as bentonite, hectorite, saponite, beiderite, nontronite, stevensite, beidellite, montmorite, swellable synthetic mica, swellable synthesis Examples include smectite. The swellable inorganic layered compound has a laminated structure consisting of unit crystal lattice layers with a thickness of 1 to 1.5 nm, and the lattice layer is insufficiently positively charged because the substitution of metal atoms in the lattice is significantly larger than other clay minerals. In order to compensate for this, cations such as Na ⁺ , Ca ²⁺ and Mg ²⁺ are adsorbed between the layers. The cations present between these layers are called exchangeable cations and exchange with various cations. In particular, when the cation between layers is Li ⁺ , Na ⁺ or the like, since the ionic radius is small, the bond between the layered crystal lattices is weak, and the layer swells greatly with water. If shear is applied in this state, it will easily cleave and form a stable sol in water. Bentonite and swellable synthetic mica are preferred in that this tendency is strong. In particular, water-swellable synthetic mica is preferable.

Examples of water-swellable synthetic mica include Na tetrathic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ Na, Li teniolite (NaLi) Mg ₂ (Si ₄ O ₁₀ ) F ₂ Na, or Li hectorite (NaLi). / 3Mg ₂ / 3Li _1/3 Si ₄ O ₁₀ ) F _{2 and the} like.
The water-swellable synthetic mica preferably has a thickness of 1 to 50 nm and a surface size of 1 to 20 μm. For diffusion control, the thinner the better, the better the plane size, as long as the smoothness and transparency of the coated surface are not deteriorated. Therefore, the aspect ratio is preferably 100 or more, more preferably 200 or more, and particularly preferably 500 or more.

When the water-swellable synthetic mica is used, the mass ratio x / y between the mass (solid content) x of the binder in the first layer and the mass y of the water-swellable synthetic mica is preferably in the range of 1 to 30. The range of 5 or more and 15 or less is more preferable. When the mass ratio is within the above range, the effect is great in suppressing oxygen permeation and blistering.
In addition, well-known additives, such as antioxidant, can also be added to a 1st layer.

  The thickness of the first layer is preferably in the range of 1 to 30 μm, and more preferably in the range of 5 to 20 μm. When the thickness of the first layer is within the above range, the glossiness of the surface when calendering is performed later is improved, whiteness can be obtained with a small amount of white pigment, and handleability such as bendability. Can be equivalent to coated paper or art paper.

(Second layer)
The recording medium of the present invention further has a second layer on the first layer on the base paper.
The second layer includes at least a white pigment and a compound having two or more amino groups in the molecule, and has a water absorption amount of 2 mL / m ^{2 on} the surface of the second layer at a contact time of 0.5 seconds according to the Bristow method. The amount is 8 mL / m ² or less. If it is this range, there will be no restriction | limiting in particular, As a 2nd layer, it can select suitably from well-known things according to the objective.
In addition, the second layer can be constituted by using other components such as a thermoplastic resin as necessary.

  The second layer in the present invention includes, for example, a layer further containing a thermoplastic resin, a layer further containing a thermoplastic resin having a solid mass of 10 to 60 parts per 100 parts by weight of a white pigment, and a pH of the layer surface of 4. The following layers are preferred.

-White pigment-
The second layer contains at least one white pigment. By containing the white pigment, the ink (particularly the pigment in the ink) can be retained in the second layer, and the background whiteness is also increased.

The white pigment is not particularly limited. For example, calcium carbonate, kaolin, titanium dioxide, aluminum trihydroxide, zinc oxide, barium sulfate, satin white, talc and the like are generally used as white pigments for coated paper for printing. You can choose from.
The preferable range of the particle size of the white pigment in the second layer is the same as the particle size of the white pigment in the first layer.

  Of these, kaolin is particularly preferable in terms of preventing image bleeding and color mixing between colors. Examples of kaolin include Kaoblite 90 manufactured by Shiroishi Calcium Co., Ltd., kao gloss, kao white, and the like.

  When an image is formed by applying the recording medium of the present invention to the inkjet recording method of the first or second aspect of the present invention described later, that is, the pH of the surface of the second layer is set to the acidic side (preferably 4 or less). ), Or when performing ink drawing using a treatment liquid containing an acidic substance, which will be described later, from the viewpoint of avoiding bleeding and color mixing of the image when the ink is drawn, the content of calcium carbonate is the second layer. 5 mass% or less of all the pigments in it are preferable, 1 mass% or less is still more preferable, and the case where calcium carbonate is not contained is more preferable.

  As content in the 2nd layer of a white pigment, 75-99 mass% is preferable with respect to the total solid of a 2nd layer, and 80-96 mass% is more preferable.

-Compound having an amino group-
The second layer contains at least one compound having two or more amino groups in the molecule. This compound forms a covalent bond with the cross-linking agent contained in the first layer provided between the second layer and the base paper, thereby improving water resistance and generating cracks and the like. A suppressed and good surface shape is obtained.

  A compound having two or more amino groups in the molecule is a compound having at least two primary or secondary amino groups not adjacent to the carbonyl group in the molecule, for example, carbon such as ethylenediamine, propylenediamine, hexamethylenediamine, etc. Alkylene diamine having an alkylene group of about 1 to 10; diethylenetriamine, triethylenetetramine, pentaethylenehexamine, tetraethylenepentamine, iminobispropylamine, 3-azahexane-1,6-diamine, 4,7-diazadecane-1 Polyalkylene polyamines such as 1,10-diamine; alicyclic polyamines such as isophorone diamine and bis (aminomethyl) cyclohexane; heterocyclic polyamines and the like.

  Here, the heterocyclic polyamine is usually a polyamine having an alicyclic heterocyclic ring having at least one heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom, and a primary or secondary amino group, The nitrogen atom contained in the heterocyclic ring of the heterocyclic polyamine may be a primary or secondary amino group. Specifically, heterocyclic polyamines containing at least two secondary amino groups in the heterocyclic ring such as piperazine and homopiperazine; N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminopropyl) Examples include heterocyclic polyamines containing aminoalkyl groups such as piperazine.

  Furthermore, the compound having two or more amino groups in the molecule includes gelatin. Gelatin is produced by treatment with hydrochloric acid in the production process from collagen (Ocein) made from pork skin, beef bone, etc. and passed through a decalcification process. It is called acidic gelatin or acid-treated gelatin. is there. In addition to the acidic method gelatin produced by the above treatment, the acidic method gelatin is a low molecular weight acidic method gelatin obtained by hydrolysis or enzymatic decomposition of the acidic method gelatin produced by the above treatment, phthalated gelatin, acyl Also included are acidic gelatins that have been chemically modified, such as gelatinized gelatin, phenylcarbamylated gelatin, acetylated gelatin, succinylated gelatin, and carboxy-modified gelatin.

  Among these, as the compound having an amino group, polyalkylene polyamine, alkylamine / epihalohydrin, and gelatin are preferable from the viewpoint of water resistance and surface improvement.

A compound having two or more amino groups in the molecule may be used alone or in combination of two or more.
As content in the 2nd layer of the compound which has an amino group, 2-40 mass% is preferable with respect to the total solid of a 2nd layer, and 4-30 mass% is more preferable. When the content of the cross-linking agent is 2 or more, the water resistance of the recording medium is good, and surface quality deterioration due to cracking or the like is suppressed, and the quality of the recording medium is improved. Ink absorbency can be obtained, and the occurrence of image bleeding and color mixing can be more effectively suppressed.

-Thermoplastic resin-
The second layer may contain other components such as a thermoplastic resin in addition to the above components.
There is no restriction | limiting in particular as a thermoplastic resin, For example, the thermoplastic resin similar to what was mentioned by the above-mentioned 1st layer can be used.

-Water absorption by Bristow method-
In the present invention, the water absorption amount at a contact time of 0.5 seconds by the Bristow method on the surface of the second layer is set to 2 mL / m ² or more and 8 mL / m ² or less. When the water absorption is ² to 8 mL / m ² , the second layer is slowly permeable, delays liquid absorption on the application surface when liquid such as ink is applied, and suppresses the degree of curling. In addition, intercolor bleeding and color mixing are prevented. To prevent intercolor bleeding and color mixing, the pH of the surface of the second layer is adjusted to acidic (particularly pH 4 or lower) as described later, or when a treatment liquid containing an acidic substance described later is used together with ink. It is particularly effective.
The water absorption amount in the second layer is further preferably in the range of ² mL / m ^{2 to} 4 mL / m ² for the same reason as described above.

  The Bristow method is used as a method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (J'TAPPI). For details of the test method, see J. et al. Reference can be made to the description of TAPPI paper, pulp test method No. 51-87, “Liquid absorbency test method for paper and paperboard” (Bristow method), Papa Technical Journal 41 (8), 57-61 (1987). Here, using the test apparatus (Bristow testing machine) described above, the measurement is performed with a contact time of 0.5 seconds, and the headbox slit width of the Bristow test is adjusted according to the surface tension of the ink during the measurement. . In addition, the point where ink is removed from the back of the paper is excluded from the calculation.

~ PH ~
The second layer is preferably adjusted to have a pH of 4 or less on the surface of the layer, thereby aggregating the applied ink and improving the fixing of the ink. That is, for example, in the case of an ink containing a pigment as a coloring component, the pigment aggregates due to a change in pH when it drops on the second layer, and it is possible to prevent ink bleeding with time and color mixing between colors.

As a compound for acidifying the surface of the second layer, a compound having a phosphoric acid group, a phosphonic group, a phosphine group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, a carboxylic acid group or a salt-derived group is used. It is preferable to use a compound having a phosphoric acid group or a carboxylic acid group.
For example, the compound having a phosphate group includes phosphoric acid, polyphosphoric acid, derivatives of these compounds, or salts thereof, and the compound having a carboxylic acid group includes furan, pyrrole, pyrroline, pyrrolidone, pyrone, A compound having a pyrrole, thiophene, indole, pyridine, quinoline structure and further having a carboxyl group as a functional group, such as pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, There are thiophenecarboxylic acid, nicotinic acid, derivatives of these compounds, or salts thereof.
By adding these compounds to the film forming solution for forming the second layer, the pH can be adjusted to 4 or less. What is necessary is just to select the addition amount suitably so that pH may become 4 or less.

  The pH can be measured by the A method (coating method) of the measurement of the film surface PH determined by the Japan Paper Pulp Technology Association (J.TAPPI paper). For example, Kyoritsu Co., Ltd., which corresponds to the A method, This can be done using a PH measurement set for paper “Type MPC” manufactured by RIKEN. In the type MPC, the test liquid is spread on the paper surface and the color is measured by comparing with the standard color.

  As thickness of a 2nd layer, the range of 3-50 micrometers is preferable, and the range of 4-40 micrometers is more preferable. When the thickness of the second layer is within the above range, it is preferable in terms of preventing image bleeding and color mixing between colors.

(Other layers)
In the recording medium of the present invention, other layers other than the first and second layers may be provided as other layers. Other layers can be appropriately selected depending on the purpose.

<Method for manufacturing recording medium>
The recording medium of the present invention described above is not particularly limited as long as it can be produced so as to have a layer structure in which the first layer and the second layer are laminated in order from the base paper side on the base paper. Preferably, a coating liquid containing a crosslinking agent capable of forming a covalent bond with a compound having an amino group and a thermoplastic resin particle is applied on the base paper, and the temperature is equal to or higher than the minimum film-forming temperature of the thermoplastic resin particle. A first forming step of forming a first layer by heat treatment in a temperature region, and a film forming liquid containing a white pigment and a compound having two or more amino groups in the molecule are provided on the first layer. And a second forming step for forming the second layer (a recording medium manufacturing method of the present invention). The recording medium manufacturing method of the present invention may further include other processes appropriately selected as necessary.

-First forming step-
In the first forming step, a film-forming liquid (first film-forming liquid for layer formation) containing a crosslinking agent capable of forming a covalent bond with a compound having an amino group and thermoplastic resin particles is formed on the base paper. The first layer is formed by applying and heat-treating in a temperature range equal to or higher than the minimum film-forming temperature of the thermoplastic resin particles. Note that pressure may be applied in the heat treatment.

The details of the crosslinking agent capable of forming a covalent bond between the base paper and the compound having an amino group are as described in the first layer described above, and the preferred embodiments are also the same.
Examples of the thermoplastic resin and particles thereof are the same as those of the thermoplastic resin that can be used in the first layer and the latex thereof, and are not particularly limited. The thermoplastic resin particles may be used alone or in combination of two or more.

  The thermoplastic resin particles preferably have an average particle size of 10 to 200 nm. Here, the average particle diameter of the thermoplastic resin particles is a value measured by a dynamic light scattering method (device name: ELS-800, manufactured by Otsuka Electronics Co., Ltd.).

The thermoplastic resin constituting the thermoplastic resin particles preferably has a minimum film-forming temperature (MFT) of 5 ° C to 60 ° C.
The coating amount of the thermoplastic resin is preferably ¹ to 30 g / m2.

  As the thermoplastic resin particles, those containing water-dispersible latex-dispersed particles are preferable from the viewpoints of suppression of cockling, improvement of bleeding over time, production suitability, and the like. The water-dispersible latex is obtained by dispersing a hydrophobic polymer insoluble or hardly soluble in water as fine particles in a water-phase dispersion medium. This dispersion state may be a polymer that is emulsified in a dispersion medium, an emulsion polymerized, a micelle-dispersed, or a polymer molecule that has a partially hydrophilic structure and the molecular chain itself is molecular. Any of those dispersed may be used. For such water-dispersible latexes, edited by Taira Okuda and Hiroshi Inagaki “Synthetic Resin Emulsion” (published by Kobunshi Publishing Co., Ltd., 1978), Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki and Keiji Kasahara Published by Kobunshi Shuppankai, 1993) and Soichi Muroi, “Chemistry of Synthetic Latex” (published by Kobunshi Shuppankai, 1970).

  Specific examples of the water-dispersible latex include polyester urethane latex, acrylic latex, acrylic silicone latex, acrylic epoxy latex, acrylic styrene latex, acrylic urethane latex, styrene-butadiene latex, and acrylonitrile. Preferable examples include at least one selected from butadiene latex and vinyl acetate latex.

The molecular weight of the water-dispersible latex is preferably 3,000 to 100,000 in terms of number average molecular weight, and more preferably about 5,000 to 100,000. When the molecular weight is 3,000 or more, the mechanical strength of the first layer can be secured, and when the molecular weight is 100,000 or less, it is advantageous in terms of production suitability such as dispersion stability and viscosity.
Among the water-dispersible latexes, the first layer is selected from polyester-based urethane latex and acrylic silicone-based latex from the viewpoint that the ink solvent permeability and the effect of suppressing cockling are high and the economy and manufacturing suitability can be combined. 1 type or 2 types or more are most preferable.

The application of the first layer-forming film-forming liquid is not particularly limited as long as it is a film-forming method, and can be performed by any known method such as a coating method, an ink-jet method, or an immersion method. In view of the smoothness of the film surface, it is preferable to use a coating method using the first layer-forming film forming solution as a coating solution.
As the coating method, a known coating method can be applied. Examples of the known coating method include a blade coating method, a slide bead method, a curtain method, an extrusion method, an air knife method, a roll coating method, and a Ked bar coating method. Is mentioned.

  After coating, the coating film formed by coating is heat-treated in a temperature region that is equal to or higher than the minimum film forming temperature of the thermoplastic resin. The heat treatment may be performed in combination with the drying treatment after coating, or may be performed separately. The heat treatment can be performed, for example, by a method such as placing in an oven having a temperature equal to or higher than the minimum film-forming temperature or applying a drying air having a temperature equal to or higher than the minimum film-forming temperature.

-Second forming step-
In the second forming step, a film-forming solution containing a white pigment and a compound having two or more amino groups in the molecule (for forming the second layer) on the first layer formed in the first forming step. Film-forming solution) is applied to form a second layer. There is no restriction | limiting in particular except forming a 2nd layer on a 1st layer, According to the objective, it can select suitably.

The application of the second layer forming film forming liquid is not particularly limited as long as it is a film forming method, and can be performed by any known method such as a coating method, an ink jet method, or an immersion method. It is preferable to use a coating method using the second layer-forming film forming solution as a coating solution in that the film surface is smooth and high gloss is obtained.
As a coating method, a known coating method can be applied. Examples of the known coating method include a blade coating method (vent method, bevel method), a slide bead method, a curtain method, an extrusion method, an air knife method, and roll coating. Examples thereof include a method and a Ked bar coating method. Among these, the blade coating method is more preferable because high-speed coating is possible and, for example, when a flat pigment such as a layered inorganic compound is used, gloss can be obtained by promoting its orientation. In addition, the blade coating method generates a relatively large shear stress at the moment of scraping, so that a large amount of water can easily move into the paper support due to the pressurization and penetration due to the instantaneous nip pressure, but the solvent penetration is blocked. The recording medium of the present invention having the first layer is particularly effective.

  In addition to the above steps, other steps may be provided without particular limitation. Other steps can be appropriately selected according to the purpose.

<Inkjet recording method>
The ink jet recording method of the present invention includes an ink drawing process in which ink is applied to the recording medium of the present invention described above, and ink is drawn according to predetermined image data, and an ink solvent in the ink drawn ink is dried and removed. And a drying and removing step to be configured.

  In the ink jet recording method of the present invention, for example, in the above-described recording medium of the present invention, the second layer (coating layer on the first layer) is preliminarily incorporated with an aggregating agent (treatment liquid), and the layer surface. An ink jet recording method (see FIG. 2; hereinafter referred to as “the ink jet recording method according to the first embodiment”) in which ink drawing or the like is performed on a recording medium having a lowered pH, and the recording medium of the present invention described above. On the other hand, there is an ink jet recording method (see FIG. 3; hereinafter referred to as “ink jet recording method according to the second embodiment”) in which ink drawing or the like is performed after supplying a treatment liquid containing an acidic substance (pre-coating).

The ink jet recording method according to the first aspect of the present invention is an ink for applying ink to a recording medium of the present invention in which the surface of the second layer is adjusted to a pH of 4 or less and drawing ink according to predetermined image data. A drawing process and a drying / removing process for drying and removing the ink solvent in the ink-drawn recording medium are provided.
In addition, the ink jet recording method according to the second aspect of the present invention includes a processing liquid supply step of supplying a processing liquid containing an acidic substance to the recording medium of the present invention described above, and the recording medium supplied with the processing liquid. And an ink drawing step for drawing ink in accordance with predetermined image data, and a drying removal step for drying and removing the ink solvent in the ink-drawn recording medium.
Any of the inkjet recording methods according to the first and second aspects described above may further include other steps selected as appropriate.

-Ink drawing process-
The ink drawing process of the first aspect uses the recording medium of the present invention in which the layer surface of the second layer is adjusted to pH 4 or less, among the recording media of the present invention described above. By applying ink to the layer, ink is drawn according to predetermined image data. When ink (for example, pigment ink) is applied to the second layer, the ink (for example, pigment in the ink) aggregates due to pH change at the time of landing, thereby preventing ink bleeding and color mixing between colors. The

  In the ink drawing step of the second aspect, the processing liquid is supplied in the following processing liquid supply step without adjusting or adjusting the layer surface pH of the second layer to 4 or less as in the first aspect. By applying ink to the recording medium, ink drawing is performed according to predetermined image data. In the second aspect, at least a part of the second layer is in an acidic state (preferably pH 4 or less) by the treatment liquid supplied to the second layer before applying the ink or simultaneously with applying the ink. The ink applied here (for example, pigment ink) undergoes a pH change at the time of landing, causing aggregation in the ink (for example, pigment in the ink), thereby preventing ink bleeding and color mixing between colors.

The ink drawing process is not particularly limited except that ink is drawn according to predetermined image data, and can be appropriately selected according to the purpose. For example, ink can be drawn by ejecting ink by an inkjet method. There are no particular restrictions on the ink jet recording system, for example, a charge control system that ejects ink using electrostatic attraction, a drop-on-demand system (pressure pulse system) that uses the vibration pressure of a piezo element, and an electrical signal. Either an acoustic ink jet method that irradiates ink using an acoustic beam instead of an acoustic beam and ejects ink using radiation pressure, or a thermal ink jet method that uses ink to form bubbles by heating ink and generate pressure. May be. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent. A method using ink.
Among these, the drop-on-demand method (pressure pulse method) using a piezoelectric element is suitable.

-Processing liquid supply process-
In the ink jet recording method according to the second aspect, a treatment liquid supply step is provided before the ink drawing step, and a treatment liquid containing an acidic substance is supplied in advance to the second layer of the recording medium. The treatment liquid supply step is not particularly limited except that a treatment liquid containing the following acidic substance is supplied, and can be appropriately selected according to the purpose. Further, this treatment liquid supply step may be provided in the ink jet recording method according to the first aspect, if necessary.

(Processing liquid)
The treatment liquid containing an acidic substance may be any liquid that contains an acidic substance and is adjusted so as to have acidity, and is preferably an aqueous treatment liquid in which an acidic substance is mixed with an aqueous medium. The pH of the treatment liquid in the present invention is preferably 4 or less from the viewpoint of preventing ink bleeding and color mixing between colors.

Examples of the acidic substance for constituting the treatment liquid acidic include a phosphate group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, a sulfinic acid group, a carboxylic acid group, or a group derived from a salt thereof. A compound having a phosphoric acid group or a carboxylic acid group is more preferable, and a compound having a carboxylic acid group is still more preferable.
For example, the compound having a phosphate group includes phosphoric acid, polyphosphoric acid, derivatives of these compounds, or salts thereof, and the compound having a carboxylic acid group includes furan, pyrrole, pyrroline, pyrrolidone, pyrone, A compound having a pyrrole, thiophene, indole, pyridine, quinoline structure and further having a carboxyl group as a functional group, such as pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, Thiophenecarboxylic acid, nicotinic acid, derivatives of these compounds, or salts thereof are added to the treatment liquid.

  Moreover, as said acidic substance, it is preferable that they are pyrrolidone carboxylic acid, pyrone carboxylic acid, furan carboxylic acid, coumaric acid, or these compound derivatives, or these salts. In addition, an acidic substance may be used by 1 type and may be used together 2 or more types.

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

  The treatment liquid may be supplied to the entire recording surface of the recording medium, or may be supplied according to at least a part of the recording surface, for example, predetermined image data. Moreover, there is no restriction | limiting in particular in the supply method of a process liquid, A coating method, an inkjet method, a dipping method etc. are mentioned, For example, you may discharge and supply a process liquid by the inkjet method.

  In the ink jet recording method according to the second aspect, drawing may be performed using an aqueous two-liquid aggregation ink described later.

-Dry removal process-
In the drying and removing step, the ink solvent in the recording medium on which ink has been drawn is removed by drying. There is no particular limitation other than drying and removing the ink solvent of the ink applied to the recording medium, and it can be appropriately selected according to the purpose.
In the recording medium of the present invention, the drying removal step is performed in a state where the ink solvent (particularly water) is present near the surface of the recording medium because the coat layer as the second layer is slowly permeable. The drying and removal can be performed by, for example, a method of applying a drying air at a predetermined temperature, a method of passing a heated and / or pressurized roll pair, or the like.

-Other processes-
The inkjet recording method of the present invention may be provided with other steps in addition to the above steps. There is no restriction | limiting in particular as another process, According to the objective, it can select suitably. For example, a heat fixing step may be mentioned.

  The ink jet recording method of the present invention may be provided with a heat fixing step for melting and fixing latex particles contained in, for example, the ink used in the ink jet recording method after the drying and removing step. By this heat fixing step, the fixing property of the ink to the recording medium can be improved. The heat fixing step is not particularly limited except for the above-described melt fixing, and can be appropriately selected according to the purpose.

-Aspect example of first ink jet recording method-
In the first ink jet recording method, for example, ink drawing, drying (water drying, blow drying), and heat fixing can be performed under the following conditions.
<Ink drawing>
Head: 1,200 dpi / 20 inch width full line head Discharge droplet volume: 4-value recording of 0, 2.0, 3.5, 4.0 pL Driving frequency: 30 kHz (recording medium conveyance speed 635 mm / sec)
<Drying (water drying, blow drying)>
Wind speed: 8-15m / s
Temperature: 40-80 ° C
Air blowing area: 640 mm (drying time 1 second)
<Heat fixing>
Silicone rubber roller (hardness 50 °, nip width 5mm)
Roller temperature: 70-90 ° C
Pressure: 0.5-2.0 MPa

-Aspect example of second ink jet recording method-
In the second ink jet recording method, for example, pre-coating, ink drawing, drying (water drying, blow drying), and heat fixing can be performed under the following conditions.
<Processing liquid head for precoat module>
Head: 600 dpi / 20 inch full line head Discharge droplet volume: 0, 4.0 pL binary recording Drive frequency: 15 kHz (recording medium conveyance speed 635 mm / sec)
Drawing pattern: In the ink drawing process, a pattern in which a treatment liquid is applied in advance to a position for drawing at least one color ink is applied.
<Water drying for precoat module (air drying)>
Wind speed: 8-15m / s
Temperature: 40-80 ° C
Air blowing area: 450 mm (drying time 0.7 seconds)
<Ink drawing>
Head: 1200 dpi / 20 inch width full line head Discharged droplet amount: 4-value recording of 0, 2.0, 3.5, 4.0 pL Driving frequency: 30 kHz (recording medium conveyance speed 635 mm / sec)
<Drying (water drying, blow drying)>
Wind speed: 8-15m / s
Temperature: 40-80 ° C
Air blowing area: 640 mm (drying time 1 second)
<Heat fixing>
Silicone rubber roller (hardness 50 °, nip width 5mm)
Roller temperature: 70-90 ° C
Pressure: 0.5-2.0 MPa

-Aqueous two-liquid aggregation ink-
In the ink jet recording method according to the second aspect, an aqueous two-liquid aggregation ink comprising a treatment liquid and an ink that reacts and aggregates with the treatment liquid may be used.
As the treatment liquid for the aqueous two-liquid aggregation ink, the same treatment liquid as described above can be used. Details of the treatment liquid are as described above.

-Ink-
The ink constituting the aqueous two-liquid aggregation ink can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone. Further, red, green, blue, and white inks other than yellow, magenta, and cyan color inks, and so-called special color inks (for example, colorless) in the printing field can be used. Examples of the ink include those containing latex particles, an organic pigment, a dispersant, and a water-soluble organic solvent, and further containing other additives as necessary.

<Latex particles>
Examples of the latex particles include particles such as a polymer of a compound composed of a nonionic monomer, an anionic monomer, and a cationic monomer dispersed in an aqueous medium.

  The said nonionic monomer means the monomer compound which does not have a dissociative functional group. In the broad sense, the monomer compound means a compound that is polymerized alone or with another compound. The monomer compound is preferably a monomer compound having an unsaturated double bond.

  The anionic monomer means a monomer compound containing an anionic group that can have a negative charge. The anionic group may be any as long as it has a negative charge, but is preferably a phosphate group, phosphonic acid group, phosphinic acid group, sulfuric acid group, sulfonic acid group, sulfinic acid group or carboxylic acid group. More preferably a phosphoric acid group or a carboxylic acid group, and even more preferably a carboxylic acid group.

  The cationic monomer means a monomer containing a cationic group that can have a positive charge. The cationic group may be any as long as it has a positive charge, but is preferably an organic cationic substituent, and more preferably a nitrogen or phosphorus cationic group. Further, it is more preferably a pyridinium cation or an ammonium cation.

<Organic pigment>
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 222, C.I. 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 U.S. 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.

  Further, the average particle diameter of the organic pigment is preferably as small as possible from the viewpoint of transparency and color reproducibility, but is preferably large from the viewpoint of light resistance. As an average particle diameter which balances these, 10-200 nm is preferable, 10-150 nm is more preferable, 10-100 nm is further more preferable. In addition, the particle size distribution of the organic pigment is not particularly limited, and may be either a wide particle size distribution or a monodispersed particle size distribution. Two or more kinds of organic pigments having a monodispersed particle size distribution may be mixed and used.

  The addition amount of the organic pigment is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, further preferably 5 to 20% by mass, and particularly 5 to 15% by mass with respect to the ink. preferable.

<Dispersant>
The organic pigment dispersant may be a polymer dispersant or a low molecular surfactant type dispersant. The polymer dispersant may be either a water-soluble dispersant or a water-insoluble dispersant.

  The low molecular surfactant type dispersant is added for the purpose of stably dispersing the organic pigment in an aqueous solvent while keeping the ink at a low viscosity. The low molecular dispersant is a low molecular dispersant having a molecular weight of 2,000 or less. The molecular weight of the low molecular dispersant is preferably 100 to 2,000, more preferably 200 to 2,000.

  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.

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

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

  Moreover, when a low molecular dispersing agent has an anionic hydrophilic group, it is preferable that pKa is 3 or more from a viewpoint of making it contact with an acidic process liquid and promoting an aggregation reaction. The pKa of the low molecular dispersant in the present invention is determined experimentally from a titration curve by titrating a solution obtained by dissolving 1 mmol / 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. If the pKa of the low molecular dispersant is 3 or more, theoretically, 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. Also from this viewpoint, the low molecular dispersant preferably has a carboxylic acid group as an anionic group.

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

  Of 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.

  For hydrophilic polymer compounds modified from natural products, fiber polymers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose, starch starches such as sodium starch glycolate and sodium phosphate phosphate Examples include molecules, seaweed polymers such as sodium alginate and propylene glycol alginate.

  Examples of the synthetic water-soluble polymer compound include vinyl polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl methyl ether, non-crosslinked polyacrylamide, polyacrylic acid or alkali metal salts thereof, water-soluble styrene acrylic resins, and the like. Acrylic resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalene sulfonic acid formalin condensate, quaternary ammonium and amino And a polymer compound having a salt of a cationic functional group such as a group in the side chain, a natural polymer compound such as shellac, and the like.

  Among these, those having a carboxyl group introduced from a homopolymer of acrylic acid, methacrylic acid or styrene acrylic acid or a copolymer of a monomer having another hydrophilic group are particularly preferred as the polymer dispersant.

  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 (meth) acrylate- (meth) acrylic acid copolymer, vinyl acetate-maleic acid copolymer Examples thereof include a polymer and a styrene-maleic acid copolymer.

  The weight average molecular weight of the dispersant is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 40,000, and particularly preferably 10,000 to 40,000. It is.

  The mixing mass ratio of the organic pigment and the 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, and still more preferably 1: 0.125. ~ 1: 1.5.

<Water-soluble organic solvent>
The water-soluble organic solvent is used for the purpose of preventing drying and promoting wetting.
A water-soluble organic solvent as a drying inhibitor is suitably used at an ink jet port of a nozzle in an ink jet recording system, and prevents clogging due to drying of the ink for ink jet.

  As the drying inhibitor, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples of such an anti-drying agent include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6- Hexanetriol, acetylene glycol derivatives, polyhydric alcohols such as glycerin, trimethylolpropane, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, etc. Lower alkyl ethers of polyhydric alcohols, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, Methyl sulfoxide, sulfur-containing compounds such as 3-sulfolene, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, the drying inhibitor is preferably a polyhydric alcohol such as glycerin or diethylene glycol. Moreover, said drying inhibitor may be used independently or may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  In addition, a water-soluble organic solvent as a penetration accelerator is preferably used for the purpose of allowing the ink to penetrate better into the recording medium (printing paper). Specific examples of such penetration enhancers include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic properties. A surfactant or the like can be suitably used. These penetration enhancers exhibit a sufficient effect when contained in the ink composition in an amount of 5 to 30% by mass. Further, it is preferable that the penetration enhancer is used within a range of an addition amount that does not cause printing bleeding and paper loss (print through).

  In addition to the above, the water-soluble organic solvent is also used for adjusting the viscosity. Specific examples of water-soluble 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, a water-soluble organic solvent may be used independently and may use 2 or more types together.

<Other additives>
Examples of the other additives include a drying inhibitor (wetting agent), an antifading agent, an emulsion stabilizer, a penetration accelerator, an ultraviolet absorber, an antiseptic, an antifungal agent, a pH adjuster, a surface tension adjuster, Well-known additives, such as an antifoamer, a viscosity modifier, a dispersing agent, a dispersion stabilizer, an antirust agent, a chelating agent, are mentioned. In the case of water-soluble ink, these various additives are added directly to the ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

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

The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 151
62, no. 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 US Pat. No. 15,162, and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 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 an amount of 0.02 to 1.00% by weight in the ink.

  As the pH adjuster, a neutralizer (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the inkjet ink, the pH adjuster is preferably added so that the inkjet ink has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10.

  Examples of the surface tension adjusting agent include nonionic surfactants, cationic surfactants, anionic surfactants, betaine surfactants, and the like.

  In addition, the addition amount of the surface tension adjusting agent is preferably an addition amount that adjusts the surface tension of the ink to 20 to 60 mN / m, and preferably an addition amount that is adjusted to 20 to 45 mN / m, in order to eject droplets well by inkjet. More preferable is an addition amount adjusted to 25 to 40 mN / m.

  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.

  Further, pages (37) to (38) of JP-A-59-157636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  Also, fluorine (fluorinated alkyl) surfactants, silicone surfactants, and the like described in JP-A Nos. 2003-322926, 2004-325707, and 2004-309806 are disclosed. By using, the abrasion resistance can be improved.

  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.

  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” and “%” are based on mass, and “polymerization degree” represents “average polymerization degree”.

Example 1
<Preparation of inkjet recording medium>
(Preparation of first layer-forming coating solution)
A polyfunctional epoxy compound (trade name: 66.2 parts of 35% acrylic latex aqueous dispersion (glass transition temperature 60 ° C., minimum film-forming temperature 50 ° C .; trade name: Aquabrid 4635, manufactured by Daicel Chemical Industries, Ltd.) : Denacol EX614B, manufactured by Nagase Chemtech Co., Ltd .; 0.7 part of a cross-linking agent capable of forming a covalent bond with a compound having an amino group, and Emulgen 109P (manufactured by Kao Co., Ltd.) 10% aqueous solution 0. 8 parts were added to prepare a first layer forming coating solution having a final solid content concentration of 24.0%.

(Preparation of second layer forming coating solution A)
100 parts of kaolin (trade name: Kaoblite 90, manufactured by Shiraishi Calcium Co., Ltd.) and 1.2 parts of 40% sodium polyacrylate (trade name: Aron T-50, manufactured by Toagosei Co., Ltd.) are mixed. And NBK-2 manufactured by Nippon Seiki Seisakusho Co., Ltd., dispersed in water, and 20% polyallylamine (trade name: PAA-03, manufactured by Nittobo Co., Ltd .; two or more amino groups in the molecule) Compound) 35 parts of an aqueous solution and 3.7 parts of 10% aqueous solution of Emulgen 109P (manufactured by Kao Corporation), and a second layer-forming coating solution A having a final solid content concentration of 27% is added. Prepared.

(Formation of the first layer)
Using an extrusion die coater, the first layer-forming coating solution obtained on both sides of high-quality paper (trade name: Shiraoi, manufactured by Nippon Paper Industries Co., Ltd.) with a basis weight of 81.4 g / m ² The first layer was formed by coating each side while adjusting the dry mass per side to 8.0 g / m ² and drying at a temperature of 85 ° C. and a wind speed of 15 m / sec for 1 minute. Furthermore, the soft calendar process shown below was performed with respect to the formed 1st layer. The thickness of the formed first layer was 7.2 μm.

~ Soft calendar processing ~
Using a soft calender provided with a roll pair in which a metal roll and a resin roll are paired with respect to the high quality paper having the first layer formed on the paper surface, the surface temperature of the metal roll is 50 ° C., and the nip pressure is 50 kg / cm. The soft calendar process was performed under the conditions described above.

(Formation of second layer)
After the soft calendering treatment, the second layer-forming coating solution A prepared above is applied to both sides of the fine paper on which the first layer is formed, using an extrusion die coater, and the dry mass per side is 20 g. / M ² was applied one side at a time and dried at a temperature of 70 ° C. and a wind speed of 10 m / sec for 1 minute to form a second layer. Further, the soft calendar process was performed on the second layer in the same manner as in the first layer. The thickness of the formed second layer was 20.4 μm.
The ink jet recording medium of the present invention was produced as described above.

(Evaluation)
The following evaluations 1 to 5 were performed on the obtained ink jet recording medium. The evaluation results are shown in Table 1 below.

-1. Cobb water absorption test
In accordance with a water absorption test based on JIS P8140, the water absorption rate on the first layer surface of the fine paper on which the first layer was formed (the amount of water penetration g when contacted with water at 20 ° C. for 120 seconds) / M ² ) was measured.

-2. Water absorption test after second layer coating-
Based on the Bristow method, the measurement was performed as follows.
A sample piece of the second layer obtained by cutting the obtained inkjet recording medium into A6 size was placed on a measuring board. After the head filled with the test solution was brought into contact with the installed sample piece, the liquid absorption characteristics were measured by automatically scanning a scanning line (from inside to outside) as shown in FIG. The measurement board changed the rotation speed (contact time between paper and ink) stepwise and rotated to obtain the relationship between the contact time and the liquid absorption amount (water absorption amount). Table 1 below shows the water absorption at a contact time of 0.5 seconds.

-3. Curl test
A 50 mm × 5 mm size test piece is prepared by cutting the ink jet recording medium, and is applied to the test piece so that the water is 10 g / m ² in the MD and CD directions, and the JAPAN TAPPI paper pulp test method No. . 15-2: 2000 (Paper-Curl Test Method-Part 2) In accordance with the curl curvature measurement method defined in 15-2: 2000, the curl degree after standing for 8 hours at 23 ° C. and 50% RH is as follows. Evaluation was made according to criteria.
<Evaluation criteria>
A: The curl degree was less than 10.
B: The curl degree was 10 or more and less than 20.
C: Curling degree was 20 or more and less than 30.
D: Curling degree was 30 or more.

-4. Water resistance test
After dropping water on the obtained ink jet recording medium, the state of the layer of the ink jet recording medium after 30 seconds had passed and the water was wiped off with tissue paper was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: No peeling of the layer was observed.
B: A part of the layer was peeled off.
C: The second layer was almost peeled off.

-5. Surface evaluation-
The surface state of the obtained inkjet recording medium was visually observed and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: No cracking was observed in the layer.
B: Cracks were observed in part of the layer.
C: Many cracks were observed in the layer.

<Preparation of ink>
(1) Preparation of Cyan Pigment Ink C-Preparation of Pigment Dispersion-
A dispersion was prepared by stirring and mixing 10 g of cyanine blue A-22 (PB15: 3) manufactured by Dainichi Seika Co., Ltd., 10.0 g of the following low molecular weight dispersant, 4.0 g of glycerin, and 26 g of ion-exchanged water. Next, using an ultrasonic irradiation device (Vibra-cell VC-750, manufactured by SONICS, tapered microchip: φ5 mm, Amplitude: 30%), the dispersion is intermittently irradiated with ultrasonic waves (irradiation 0.5 seconds, pause) (1.0 second) for 2 hours to further disperse the pigment to obtain a 20% by mass pigment dispersion.

Apart from the pigment dispersion, the following compounds were weighed, stirred and mixed to prepare a mixture I.
・ Glycerin ... 5.0g
・ Diethylene glycol: 10.0 g
・ Orphine E1010 (manufactured by Nissin Chemical Industry) ・ ・ ・ 1.0g
・ Ion-exchanged water ... 11.0 g

This mixed liquid I was slowly dropped into 23.0 g of a stirred 44% SBR dispersion (polymer fine particles: 3% acrylic acid, Tg (glass transition temperature) 30 ° C.) and stirred and mixed to prepare mixed liquid II. did.
Next, this mixed liquid II was stirred and mixed while slowly dropping into the above-mentioned 20% by mass pigment dispersion to prepare 100 g of cyan pigment ink C (cyan ink). When the pH of the pigment ink C prepared as described above was measured using a pH meter WM-50EG manufactured by Toa DKK, the pH value was 8.5.

(2) Preparation of Magenta Pigment Ink M In the preparation of Pigment Ink C, Chromatic Jet Magenta DMQ (PR-122) manufactured by Ciba Specialty Chemicals was used in place of the pigment used in the preparation of Pigment Ink C. Prepared a magenta pigment ink M (magenta ink) in the same manner as the pigment ink C. When the pH of the pigment ink M prepared as described above was measured with a pH meter WM-50EG manufactured by Toa DKK, the pH value was 8.5.

(3) Preparation of Yellow Pigment Ink Y In the preparation of Pigment Ink C, instead of using the pigment used for the preparation of Pigment Ink C, Ibarga Yellow GS (PY74) manufactured by Ciba Specialty Chemicals was used. Yellow pigment ink Y (yellow ink) was prepared in the same manner as the preparation of ink C. When the pH of the pigment ink Y prepared as described above was measured with a pH meter WM-50EG manufactured by Toa DKK, the pH value was 8.5.

(4) Preparation of black pigment ink K In the preparation of pigment ink C, instead of the pigment dispersion used for the preparation of pigment ink C, a dispersion CAB-O-JETTM_200 (carbon black) manufactured by CABOT was used. Except for this, a black pigment ink K (black ink) was prepared in the same manner as in the preparation of pigment ink C. When the pH of the pigment ink K prepared as described above was measured with a pH meter WM-50EG manufactured by Toa DKK, the pH value was 8.5.

<Preparation of treatment solution>
The treatment liquid was prepared by mixing the following components.
・ Phosphoric acid ... 10g
・ Glycerin 20g
・ Diethylene glycol ... 10g
・ Orphine E1010 (manufactured by Nissin Chemical Industry) ・ ・ ・ 1g
・ Ion-exchanged water ... 59g
When the pH of the treatment solution thus prepared was measured with a pH meter WM-50EG manufactured by Toa DKK Co., Ltd., the pH value was 1.0.

<Image formation and droplet ejection method and conditions>
Using the cyan pigment ink C, the magenta pigment ink M, the yellow pigment ink Y, the black pigment ink K, and the treatment liquid, a four-color single-pass image is formed using the apparatus shown in FIG. 3 under the following conditions. did. At this time, a gray scale and a character image were formed.

~ Head for treatment liquid for precoat module ~
Head: 600 dpi / 20 inch width piezo full line head Discharge droplet volume: binary recording of 0, 4.0 pL Drive frequency: 15 kHz (recording medium conveyance speed 635 mm / sec)
Drawing pattern: In the ink drawing process, a pattern that applies at least one color ink to the processing liquid in advance at the drawing position is applied.

~ Water drying for precoat module (blow drying) ~
Wind speed: 15m / s
Temperature: Heated from the back surface of the recording medium recording surface with a contact type flat heater so that the surface temperature of the recording medium becomes 60 ° C. Air blowing area: 450 mm (drying time 0.7 seconds)

~ Ink drawing ~
Head: 1,200 dpi / 20 inch width piezo full line head is arranged for 4 colors. Ejected droplet volume: 4-value recording of 0, 2.0, 3.5, 4.0 pL Drive frequency: 30 kHz (Recording medium transport speed 635 mm / sec)

~ Drying (water drying, blow drying) ~
Wind speed: 15m / s
Temperature: 60 ° C
Air blowing area: 640 mm (drying time 1 second)

-Heat fixing-
Silicone rubber roller (hardness 50 °, nip width 5mm)
Roller temperature: 90 ° C
Pressure: 0.8 MPa

Subsequently, the following evaluation 6. was performed.
-6. Evaluation of droplet ejection
The gray scale and character image formed above were visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: Image bleeding and color mixing were not observed, and “hawk” characters of 4 pt or less could be resolved.
B: No image blur or color mixing was observed, and resolution was possible up to 5 pt “hawk” characters.
C: Image blurring and color mixing were often observed, and the practicality was low.
D: Image bleeding, color mixing between colors was severe, and practicality was extremely low.

(Example 2)
In Example 1, 0.7 part of the polyfunctional epoxy compound used for the preparation of the first layer-forming coating solution was added to a 40% carbodiimide compound aqueous solution (trade name: SV02, manufactured by Nisshinbo Co., Ltd .; compound having an amino group) The ink jet recording medium of the present invention was prepared and evaluated in the same manner as in Example 1 except that 1.75 parts of a crosslinking agent capable of forming a covalent bond with the ink was replaced. The evaluation results are shown in Table 1 below.

(Example 3)
In Example 1, 0.7 part of the polyfunctional epoxy compound used for the preparation of the first layer-forming coating solution was replaced with the following compound (crosslinking agent capable of forming a covalent bond with a compound having an amino group). An ink jet recording medium of the present invention was prepared and evaluated in the same manner as in Example 1 except that 8.75 parts of an 8% aqueous solution was used. The evaluation results are shown in Table 1 below.

Example 4
In Example 3, 35 parts of a 20% polyallylamine aqueous solution used for the preparation of the second layer-forming coating solution was added to a 4% acid-treated gelatin solution (trade name: A-300, manufactured by Nitta Gelatin Co., Ltd.) 175. The ink jet recording medium of the present invention was prepared and evaluated in the same manner as in Example 3 except that the part was replaced with the part. The evaluation results are shown in Table 1 below.

(Example 5)
In Example 1, 35 parts of a 20% polyallylamine aqueous solution used for the preparation of the second layer-forming coating solution was mixed with a 20% dimethylamine / epihalohydrin polycondensate (trade name: UNISENSE KHE104L, manufactured by Senca Co., Ltd.). The inkjet recording medium of the present invention was prepared in the same manner as in Example 1 except that 40% sodium polyacrylate (trade name: Aron T-50, manufactured by Toagosei Co., Ltd.) was used instead of the parts. ,evaluated. The evaluation results are shown in Table 1 below.

(Example 6)
In Example 5, 0.7 part of the polyfunctional epoxy compound used for the preparation of the first layer-forming coating solution was added to 2,3-dihydroxy-5-methyl-1,4-dioxane (a compound having an amino group and Except that 40% sodium polyacrylate (trade name: Aron T-50, manufactured by Toagosei Co., Ltd.) was used instead of 1.4 parts of a 50% aqueous solution of a crosslinking agent capable of forming a covalent bond between the two. In the same manner as in Example 5, the inkjet recording medium of the present invention was produced and evaluated. The evaluation results are shown in Table 1 below.

(Example 7)
In Example 5, 0.7 part of the polyfunctional epoxy compound used for the preparation of the first layer-forming coating solution was replaced with 2-ethylenesulfonyl-N- [2- (2-ethylenesulfonyl-acetylamino) -ethyl]. -Instead of 17.5 parts of 4% aqueous solution of acetamide (crosslinking agent capable of forming a covalent bond with a compound having an amino group), 40% sodium polyacrylate (trade name: Aron T-50, Toagosei ( The ink jet recording medium of the present invention was produced and evaluated in the same manner as in Example 5 except that the product manufactured by (Co., Ltd.) was excluded. The evaluation results are shown in Table 1 below.

(Comparative Example 1)
In Example 4, 1.75 parts of 40% carbodiimide compound aqueous solution (trade name: SV02, manufactured by Nisshinbo Co., Ltd .; a crosslinking agent capable of forming a covalent bond with a compound having an amino group) A comparative inkjet recording medium was prepared and evaluated in the same manner as in Example 2 except that it was added to the second layer forming coating solution without being added to the forming coating solution. The evaluation results are shown in Table 1 below.

(Comparative Example 2)
In Example 4, the same procedure as in Example 2 was performed except that the 40% carbodiimide compound aqueous solution (trade name: SV02, manufactured by Nisshinbo Co., Ltd.) used for the preparation of the first layer-forming coating solution was not added. Comparative inkjet recording media were prepared and evaluated. The evaluation results are shown in Table 1 below.

(Comparative Example 3)
In Example 4, a comparative inkjet recording medium was produced in the same manner as in Example 4 except that the dry mass 20 g / m ² per side of the second layer forming coating solution was changed to 10 g / m ^2. And evaluated. The evaluation results are shown in Table 1 below.

(Comparative Example 4)
In Example 4, the kaolin used for the preparation of the second layer-forming coating solution was replaced with titanium oxide (trade name: Taipei R280, manufactured by Ishihara Sangyo Co., Ltd.). Comparative ink jet recording media were prepared and evaluated. The evaluation results are shown in Table 1 below.

(Comparative Example 5)
In Example 4, a comparative ink jet recording medium was prepared in the same manner as in Example 4 except that the dry mass per side of the first layer-forming coating solution was changed from 8.0 g / m ² to 4 g / m ^2. Were made and evaluated. The evaluation results are shown in Table 1 below.

As shown in Table 1 above, the Cobb water absorption for a contact time of 120 seconds according to a water absorption test according to JIS P8140 is 2.0 g / m ² or less, and the contact time by the Bristow method for the second layer is 0.5. In the examples in which the amount of water absorption per second was ² to 8 mL / m ² , the occurrence of curling, image bleeding and color mixing between colors was suppressed as compared with the comparative example, and the compound having an amino group and a covalent bond therewith By containing each of the crosslinkers that can be formed in separate layers, the water resistance and the surface shape were improved.

It is a schematic block diagram which shows the structural example of the recording medium of this invention. It is explanatory drawing for demonstrating an example of the inkjet recording method which concerns on the 1st aspect using the recording medium of this invention. It is explanatory drawing for demonstrating an example of the inkjet recording method which concerns on the 2nd aspect using the recording medium of this invention. It is a figure for demonstrating the scanning line of the head filled with the test liquid in a Bristow method. It is a schematic block diagram which shows the structure of the conventional recording medium.

Explanation of symbols

11 ... fine paper 12 ... solvent blocking layer (first layer)
13 ... Coat layer (second layer)
21 ... Base paper 22 ... Solvent absorption layer 100 ... Recording medium

Claims (11)

A first layer containing a cross-linking agent and a binder capable of forming a covalent bond between a base paper and a compound having an amino group, and a second layer containing a white pigment and a compound having two or more amino groups in the molecule And are sequentially stacked,
Cobb water absorption at a contact time of 120 seconds according to JIS P8140 on the surface of the first layer of the base paper provided with the first layer is 2.0 g / m ² or less, A recording medium having a water absorption of 2 mL / m ² or more and 8 mL / m ² or less at a contact time of 0.5 seconds by the Bristow method on the surface of the layer 2.   2. The compound having two or more amino groups in the molecule in the second layer is at least one selected from the group consisting of a polyalkylene polyamine, an alkylamine / epihalohydrin, and gelatin. The recording medium described in 1.   The cross-linking agent in the first layer is at least one selected from the group consisting of an epoxy compound, a compound having an active methylene group, cyanuric chloride, a formaldehyde precursor, and a carbodiimide. The recording medium according to claim 2.   The recording medium according to claim 1, wherein the binder in the first layer includes a thermoplastic resin.   The recording medium according to claim 4, wherein the thermoplastic resin is at least one selected from polyester urethane latex and acrylic silicone latex.   The recording medium according to claim 1, wherein the first layer further contains a white pigment.   The recording medium according to claim 1, wherein the white pigment is kaolin. On the base paper, a film-forming liquid containing a crosslinking agent capable of forming a covalent bond with a compound having an amino group and thermoplastic resin particles is applied, and in a temperature region above the minimum film-forming temperature of the thermoplastic resin particles. A first forming step of forming the first layer by heat treatment;
A second forming step of forming a second layer on the first layer by applying a film forming liquid containing a white pigment and a compound having two or more amino groups in the molecule;
The manufacturing method of the recording medium which manufactures the recording medium of any one of Claims 4-7.   9. The method for producing a recording medium according to claim 8, wherein the thermoplastic resin particles are at least one selected from polyester urethane latex and acrylic silicone latex. An ink drawing step of applying ink to the recording medium according to any one of claims 1 to 7 and drawing ink according to predetermined image data;
A drying and removing step of drying and removing the ink solvent in the recording medium on which ink is drawn;
An ink jet recording method comprising: A treatment liquid supply step of supplying a treatment liquid containing an acidic substance to the recording medium according to any one of claims 1 to 7,
An ink drawing step of applying ink to the recording medium supplied with the treatment liquid and drawing ink according to predetermined image data;
A drying and removing step of drying and removing the ink solvent in the recording medium on which ink is drawn;
An ink jet recording method comprising: