JP4533450B2 - Method for manufacturing ink jet recording medium - Google Patents

Description

The present invention relates to a recording material suitable for inkjet recording using liquid ink such as water-based ink or oil-based ink, or solid ink that is solid at room temperature and is melt-liquefied and used for printing. excellent relates to a method of manufacturing an ink jet recording medium, to a receiving performance.

In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the information systems have been developed and put into practical use.
Among the above recording methods, the inkjet recording method is capable of recording on a variety of recording materials, the hardware (device) is relatively inexpensive, compact, and excellent in quietness. Of course, it has been widely used in so-called home use.

In addition, with the recent increase in resolution of inkjet printers, it has become possible to obtain so-called photographic-like high-quality recorded matter. Furthermore, with the development of hardware (device), various recording sheets for ink jet recording have been developed.
The characteristics required for the recording sheet for ink jet recording are generally (1) fast drying (high ink absorption speed), and (2) ink dot diameter is appropriate and uniform. (No blurring), (3) good graininess, (4) high dot roundness, (5) high color density, (6) high chroma (dullness) (7) The light resistance, gas resistance and water resistance of the printed portion are good, (8) the whiteness of the recording sheet is high, and (9) the preservability of the recording sheet is good ( (No long-term storage, yellowing coloration, long-term storage does not cause image blur), (10) Stable deformation, good dimensional stability (curl is sufficiently small), (11) Hard running performance Is good. In addition to the above properties, glossy, surface smoothness, photographic paper-like texture similar to silver salt photography, etc. can be used for photo glossy paper used for the purpose of obtaining so-called photo-like high-quality recorded matter. Required.

As a sheet for inkjet recording satisfying the above requirements, a colorant receiving layer is formed on a support by applying a liquid containing inorganic fine particles, mordant, water-soluble resin such as PVA, and a curing agent for the water-soluble resin. (For example, refer to the following Patent Document 1) Or a liquid containing a water-soluble resin such as inorganic fine particles, metal compounds, and PVA is applied to a support, and the coating layer is water-soluble before the coating layer is completely dried. A material in which a liquid containing a resin curing agent is applied to form a color material receiving layer is known (see, for example, Patent Document 2 below).
The colorant-receiving layer in the ink jet recording sheet described in Patent Document 1 is a coating solution containing vapor phase silica, a cationic polymer having a structural unit of a polydiallylamine derivative (dimethyldiallylammonium chloride polymer), PVA, and boric acid. The ink jet recording sheet has a low image printing density and glossiness.
In the ink receiving layer (coloring material receiving layer) in the ink jet recording sheet of Patent Document 2, the ink receiving layer is composed of inorganic fine particles (for example, vapor phase silica having an average primary particle diameter of 20 nm or less), water-soluble resin (for example, PVA). And a coating solution containing a water-soluble metal salt having a valence of 2 or more is applied onto the support, and the water-soluble resin is added simultaneously with the coating or before the coated layer exhibits a reduced drying rate. A layer obtained by applying and curing a solution containing a crosslinking agent (for example, borax or boric acid) that can be crosslinked, and the ink receiving layer thus obtained can prevent cracking, but the image printing density The coating solution containing a water-soluble metal salt is not sufficiently stable.

By the way, as a mordant for fixing a dye in an ink receiving layer, an inorganic mordant such as a polyvalent metal salt is known in addition to the cationic polymer as described in Patent Document 1 (for example, the following patents). Reference 3 to Patent Document 5).
The ink receiving layer in Patent Document 3 is composed of inorganic fine particles, polyvinyl alcohol, at least two kinds of cationic polymers having a quaternary ammonium base, and a compound having a zirconium or aluminum atom in the molecule (except for zirconium oxide and aluminum oxide). ) And improved bleeding and water resistance during storage after printing with respect to water-soluble dyes without deteriorating bronzing.

The ink receiving layer in Patent Document 4 contains polyvinyl alcohol, a cationic polymer, and a compound having zirconium or an aluminum atom (excluding zirconium oxide and aluminum oxide), and the ink-receiving layer after printing with an inkjet printer. It is characterized in that the film surface pH of the surface of the ink receiving layer is 4 to 6, and improves bleeding and water resistance during storage after printing for water-soluble dyes without deteriorating bronzing. .
Further, the colorant receiving layer in Patent Document 5 is different from the compound A in which inorganic fine particles, hydrophilic binder, compound A containing zirconium atom or aluminum atom in the molecule (excluding zirconium oxide and aluminum oxide), Contains 0.1 to 10 mol% of Compound A containing a valent metal atom in the molecule, and suppresses the occurrence of bleeding when a print image using a water-soluble dye is stored without deteriorating bronzing. This is to improve the water resistance of the image.

When an inorganic mordant as described in Patent Documents 3 to 5 is used and an ink receiving layer is formed as described in Patent Document 2, cracks do not occur in the ink receiving layer, but sufficient gloss and print density are obtained. There was a problem that we couldn't.
JP 2000-2111235 (paragraphs 0055 to 0057) JP 2001-334742 A JP 2002-172850 A JP 2002-192830 A JP 2002-274013 A

The present invention has been made in view of the above problems, and its object is excellent in printing density and glossiness of images, an object to provide a method for producing a time of image bleeding is small ink jet recording medium body An object is to achieve the object.

Means for solving the above-mentioned problems are as follows. That is,
<1> In the method for producing an inkjet recording medium having an ink receiving layer on a support, the ink receiving layer is formed by at least the following steps (A) and (B). And an ink jet recording medium manufacturing method.
Step (A): a water-soluble resin, a crosslinking agent, and forming a coating layer by coating on the support a first liquid containing first of two selected from zirconium compounds and aluminum compounds 1 metal compound Step (B): A second liquid containing a second metal compound selected from a zirconium compound is applied to the coating layer before the coating layer is in the course of drying and before the coating layer exhibits reduced drying. And a step of crosslinking and curing the coating layer

<2> The method for producing an ink jet recording medium according to <1>, wherein the second liquid further contains a basic compound.

<3> The method for producing an ink jet recording medium according to <1> or <2>, wherein the first liquid further contains inorganic fine particles.

<4> The method for producing an ink jet recording medium according to any one of <1> to <3>, wherein the first liquid or the second liquid further contains a surfactant.

< 5 > The method for producing an ink jet recording medium according to any one of <2> to < 4 >, wherein the basic compound is an ammonium salt of a weak acid.

< 6 > The method for producing an inkjet recording medium according to any one of <1> to < 5 >, wherein the water-soluble resin is polyvinyl alcohol.

< 7 > The method for producing an ink jet recording medium according to any one of <1> to < 6 >, wherein the crosslinking agent is a boron compound.

<8> The is the pH of the first liquid is 6.0 or less, the ink-jet according to any one of <7>, wherein the <1>, wherein the pH of the second liquid is 7.1 or higher It is a manufacturing method of a recording medium.
<9> The content of the second metal compound in the second liquid is any one of <1> to <8>, which is 0.1 to 0.8% by mass with respect to the total mass of the second liquid. 2. A method for producing an ink jet recording medium according to item 1.

According to the present invention, excellent printing density and glossiness of the image, method for producing a temporal image bleed less ink jet recording medium body can be provided.

<Inkjet recording medium manufacturing method>
In the method for producing an ink jet recording medium having an ink receiving layer on a support, the ink receiving layer is formed by at least the following steps (A) and (B). It is a manufacturing method of a recording medium.
Process (A) The process process of apply | coating the 1st liquid containing 2 types of 1st metal compounds selected from water-soluble resin, a crosslinking agent, a zirconium compound, and an aluminum compound on a support body, and forming a coating layer. (B) A second liquid containing a second metal compound selected from a zirconium compound is applied to the coating layer before the coating layer is in the course of drying and the coating layer exhibits reduced-rate drying. Step of performing crosslinking and curing of the coating layer The method for producing the ink jet recording medium of the present invention is described in detail below.

The method for producing an ink jet recording medium of the present invention includes a first liquid (hereinafter referred to as “for ink receiving layer”) containing a water-soluble resin, a crosslinking agent, and two kinds of first metal compounds selected from a zirconium compound and an aluminum compound. A coating solution ”) on the support to form a coating layer (step (A), coating step), and during the drying of the coating layer, the coating layer is dried at a reduced rate. Step (Step (Step (C)) of applying a second liquid containing a second metal compound selected from zirconium compounds (hereinafter sometimes referred to as “basic solution”) and crosslinking and curing the coating layer. B), a curing step), and a method (Wet-On-Wet method << WOW method >>), and the coating layer coated on the support in the step (A) is a step (B) Coating layer by cross-linking and curing The ink receiving layer crosslinked and cured is formed.

  In the present invention, by applying a coating layer composed of the first liquid containing the first metal compound in advance and applying a second liquid containing the second metal compound to the coating layer, Good film-forming property capable of sufficiently forming a film is obtained, and the first metal compound and the second metal compound (and other mordant components) act as a mordant, and the ink, particularly the dye, is sufficiently mordanted to produce an image. An ink jet recording medium having excellent print density and glossiness and less blurring of images over time can be obtained.

The first metal compound contained in the first liquid is preferably an acidic metal compound, and examples thereof include polyvalent water-soluble metal salts and hydrophobic metal salt compounds. Specific examples include magnesium, aluminum, calcium, scandium, titanium, vanadium, manganese, iron, nickel, zirconium, copper, zinc, gallium, germanium, strontium, yttrium, molybdenum, indium, barium, lanthanum, cerium, praseodymium, neodymium. And salts or complexes of metals selected from samarium, europium, gadolinium, dysproprosium, erbium, ytterbium, hafnium, tungsten, bismuth.
In the present invention, the first metal compound is two kinds selected from a zirconium compound and an aluminum compound.

  Specifically, for example, calcium acetate, calcium chloride, calcium formate, zirconium acetate, zirconium tetrachloride, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate Hexahydrate, cupric chloride, ammonium copper (II) chloride dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate Tetrahydrate, nickel ammonium sulfate hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate , Aluminum chloride hexahydrate Ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zinc acetate Ammonium, zinc ammonium carbonate, titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, titanium lactate, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate , Sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, gallium nitrate, germanium nitrate, strontium nitrate, yttrium acetate, yttrium chloride , Yttrium nitrate, indium nitrate, orchid nitrate Tan, lanthanum chloride, lanthanum acetate, lanthanum benzoate, cerium chloride, cerium sulfate, cerium octylate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, dysprosium nitrate, erbium nitrate, ytterbium nitrate, hafnium chloride, nitric acid Bismuth etc. are mentioned. Among these, aluminum sulfate, aluminum alum, basic polyaluminum hydroxide, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, zirconium nitrate, and zirconium tetrachloride are preferable.

The first metal compound described above, Ru is containing two to the first liquid. Metal compounds, for dye mordanting according to the different types, it is possible to increase the mordanting capacity by the first metal compound for two types used. Thus, more specifically-form, contain a metal compound corresponding to the two dyes to be mordanted. Various combinations are conceivable as the metal compound corresponding to the dye. For example, a zirconium compound is effective for a black dye of a general ink.

  As content in the 1st liquid of a said 1st metal compound, 0.01-1 mass% is preferable with respect to the total mass of a 1st liquid, More preferably, it is 0.05-0.8 mass%. . By setting the content of the first metal compound in the above-described range, an ink jet recording medium can be produced in which curling under low humidity conditions is not deteriorated and the aging of the image is small. In addition, when using together the other mordant component mentioned later, total amount is in the said range, Comprising: It can contain in the range which does not impair the effect of this invention.

As the second metal compound contained in the second liquid, those which are stable under basic conditions can be used without limitation. The metal compound may be a metal salt, a metal complex compound, an inorganic oligomer, or an inorganic polymer. . As said metal compound, what is mentioned as an inorganic mordant mentioned later is used preferably. Of these, zirconium compounds, aluminum compounds and zinc compounds are preferable, and zirconium compounds are particularly preferable. Examples include ammonium zirconium carbonate, ammonium zirconium nitrate, potassium zirconium carbonate, zirconium ammonium citrate, zirconyl stearate, zirconyl octylate, zirconyl nitrate, zirconium oxychloride, and zirconium zirconium hydroxy chloride, with zirconium zirconium carbonate being particularly preferred. Moreover, you may use together the other mordant component mentioned later for the 2nd liquid as needed.
In the present invention, the second metal compound is a zirconium compound.

  In addition, as the metal complex compound, the metal complex described in “Chemical Review No. 32 1981” edited by the Chemical Society of Japan and “Coordination Chemistry Review”, Vol. 84, pages 85-277 (1988). And transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701 can be used.

  The content of the second metal compound in the second liquid is preferably 0.1 to 0.8 mass%, more preferably 0.2 to 0.5 mass%, based on the total mass of the second liquid. It is. By setting the content of the second metal compound in the above range, the gloss can be improved without deteriorating bronzing. In addition, when using together the other mordant component mentioned later, total amount is in the said range, Comprising: It can contain in the range which does not impair the effect of this invention.

  Next, the basic compound contained in the second liquid will be described. Basic compounds include ammonium salts of weak acids, alkali metal salts of weak acids (lithium carbonate, sodium carbonate, potassium carbonate, lithium acetate, sodium acetate, potassium acetate, etc.), alkaline earth metal salts of weak acids (magnesium carbonate, barium carbonate) , Magnesium acetate, barium acetate, etc.), alkali metal or alkaline earth metal hydroxide, hydroxyammonium, ammonia, primary to tertiary amines (ethylamine, dimethylamine, triethylamine, polyallylamine, tripropylamine, tributylamine, Hexylamine, dibutylamine, butylamine, N-ethyl-N-methylbutylamine, etc.), primary to tertiary anilines (diethylaniline, dibutylaniline, ethylaniline, aniline, etc.), pyridine optionally having a substituent (2 Aminopyridine, 3-aminopyridine, 4-aminopyridine, 4- (2-hydroxyethyl) -, etc. aminopyridine) but the like, ammonium salts of weak acids are particularly preferred.

  The weak acid is an inorganic acid or an organic acid described in Chemical Handbook Fundamentals II (Maruzen Co., Ltd.) or the like and having an pKa of 2 or more. Examples of the weak acid ammonium salt include ammonium carbonate, ammonium hydrogen carbonate, ammonium borate, and ammonium acetate. However, it is not limited to these. Among these, ammonium carbonate, ammonium hydrogen carbonate, and ammonium carbamate are preferable, and are effective in that ink bleeding can be reduced without remaining in the layer after drying. Two or more basic compounds may be used in combination.

  As content in the 2nd liquid of the said basic compound, 0.5-10 mass% is preferable with respect to the total mass containing the solvent of a 2nd liquid, More preferably, it is 1-5 mass%. When the content of the basic compound is particularly in the above range, a sufficient degree of curing can be obtained, and the ammonia concentration becomes too high and the working environment is not impaired.

As the first liquid in the step (A), for example, a coating liquid for an ink receiving layer containing gas phase method silica, polyvinyl alcohol (PVA), boric acid, a cationic resin, a nonionic or amphoteric surfactant and a high boiling point organic solvent. Can be prepared as follows. In addition, the detail of each component which comprises a 1st liquid is mentioned later.
That is, vapor phase silica is added to water, and a cationic resin is further added and dispersed with a high-pressure homogenizer or a sand mill. 3), and a nonionic or amphoteric surfactant and a high-boiling organic solvent are further added and stirred. The obtained coating liquid is a uniform sol, and a coating layer can be obtained by coating this on a support by the following coating method to form a porous ink receiving layer having a three-dimensional network structure. it can. At this time, as described above, partial gelation of PVA can be prevented by adding PVA after diluting boric acid.

  The first liquid (coating liquid for ink receiving layer) can be made into an aqueous dispersion having an average particle diameter of 10 to 300 nm by making fine particles using a disperser. Dispersers used for obtaining the aqueous dispersion include various types of conventionally known high-speed rotating dispersers, medium stirring dispersers (ball mill, sand mill, etc.), ultrasonic dispersers, colloid mill dispersers, high pressure dispersers and the like. Although a disperser can be used, a medium stirring type disperser, a colloid mill disperser, or a high-pressure disperser is preferable from the viewpoint of efficiently dispersing the formed fine particles.

  In the present invention, the first liquid is preferably an acidic solution, and the pH of the first liquid is preferably 6.0 or less, more preferably 5.0 or less, and 4.0 or less. More preferably. This pH can be adjusted by appropriately selecting the type and addition amount of the cationic resin. Moreover, you may adjust by adding an organic or inorganic acid. When the pH of the first liquid is 6.0 or less, the crosslinking reaction of the water-soluble resin by the crosslinking agent (particularly boron compound) in the first liquid can be more sufficiently suppressed.

  Application of the first liquid (ink receiving layer coating liquid) in the step (A) is, for example, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, a bar coater, etc. It can carry out by the well-known coating method using this.

  In step (B), the second liquid (basic solution) can be applied after application of the ink-receiving layer coating liquid (first liquid), but this application causes the coating layer to show reduced-rate drying. Suitably done before. That is, after the application of the first liquid, the second liquid is preferably introduced while the coating layer exhibits constant rate drying.

  The second liquid may contain a crosslinking agent and other mordant components as necessary. The second liquid can be used as an alkaline solution to promote hardening, and is preferably adjusted to pH 7.1 or higher, more preferably pH 7.5 or higher, and particularly preferably pH 7.9 or higher. If the pH is too close to the acidic side, the cross-linking reaction of the water-soluble polymer contained in the first liquid is not sufficiently performed by the cross-linking agent, resulting in the occurrence of bronzing and defects such as cracks in the ink receiving layer. is there.

  The second liquid is, for example, ion-exchanged water, a metal compound (for example, 1 to 5%), a basic compound (for example, 1 to 5%), and, if necessary, paratoluenesulfonic acid (for example, 0.5 to 3). %) And the mixture is sufficiently stirred. In addition, all "%" of each composition means solid content mass%.

  Moreover, water, an organic solvent, or these mixed solvents can be used for the solvent used for preparation of each liquid. Examples of the organic solvent that can be used for coating include alcohols such as methanol, ethanol, n-propanol, i-propanol, and methoxypropanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, acetonitrile, ethyl acetate, and toluene. .

  In the step (B), “before the coating layer comes to show reduced-rate drying” usually refers to a process for several minutes immediately after the coating of the coating liquid for the ink receiving layer. This shows a phenomenon of “constant rate drying” in which the content of the solvent (dispersion medium) in the medium decreases in proportion to time. About the time which shows this "constant rate drying", it describes in chemical engineering handbook (pages 707-712, Maruzen Co., Ltd. issue, October 25, 1980), for example.

  As described above, after the ink receiving layer coating liquid (first liquid) is applied, it is dried until the coating layer of the first liquid shows reduced-rate drying. This drying is generally performed at 40 to 180 ° C. (preferably Is carried out at 50 to 120 ° C. for 0.5 to 10 minutes (preferably 0.5 to 5 minutes). The drying time naturally varies depending on the coating amount, but usually the above range is appropriate.

  As a method of giving before the said coating layer comes to show reduction-rate drying, (1) The method of further apply | coating 2nd liquid on a coating layer, (2) The method of spraying by methods, such as a spray, (3 ) A method of immersing the support on which the coating layer is formed in the second liquid.

  In the method (1), examples of the application method for applying the second liquid include a curtain flow coater, an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, and a bar. A known coating method such as a coater can be used. However, it is preferable to use a method in which the coater does not directly contact an already formed coating layer, such as an extrusion die coater, a curtain flow coater, a bar coater or the like.

  After application of the second liquid, it is generally heated at 40 to 180 ° C. for 0.5 to 30 minutes to be dried and cured. Especially, it is preferable to heat at 40-150 degreeC for 1 to 20 minutes.

  The step (A) and the step (B) can be performed simultaneously. That is, the second liquid (basic solution) can be preferably applied at the same time as the first liquid (ink receiving layer coating liquid) is applied. In such a case, the first liquid and the second liquid are added to the second liquid (basic solution). An ink receiving layer can be formed by simultaneously applying (multilayer coating) on a support so that one liquid is in contact with the support, followed by drying and curing.

  The simultaneous coating (multilayer coating) can be performed by a coating method using, for example, an extrusion die coater or a curtain flow coater. After the simultaneous application, the formed application layer is dried. In this case, the drying is generally performed by heating the application layer at 15 to 150 ° C. for 0.5 to 10 minutes, preferably 40 to 100. It is carried out by heating at a temperature of 0.5 to 5 minutes.

  When the simultaneous coating (multilayer coating) is performed by, for example, an extrusion die coater, the two types of coating liquid discharged simultaneously are in the vicinity of the discharge port of the extrusion die coater, that is, before moving onto the support. In that state, it is coated on the support in multiple layers. Since the two-layer coating liquid layered before coating is likely to cause a cross-linking reaction at the interface between the two liquids when transferred to the support, the two liquids to be ejected are mixed in the vicinity of the discharge port of the extrusion die coater. As a result, thickening is likely to occur, which may hinder the application operation. Therefore, at the time of simultaneous application as described above, it is preferable to apply the simultaneous triple layer application with the barrier liquid (intermediate liquid) interposed between the two liquids together with the application of the first liquid and the second liquid.

  The barrier layer solution can be selected without particular limitation. For example, an aqueous solution containing a trace amount of water-soluble resin, water, or the like can be given. The water-soluble resin is used in consideration of applicability for the purpose of a thickener and the like. For example, a cellulose resin (for example, hydroxypropylmethylcellulose, methylcellulose, hydroxyethylmethylcellulose) And polymers such as polyvinylpyrrolidone and gelatin. The barrier layer liquid may contain a mordant.

  After forming the ink receiving layer on the support, the ink receiving layer is subjected to, for example, supercalendering, gloss calendering, etc., and calendering through the roll nip under heat and pressure, so that surface smoothness, glossiness, It is possible to improve transparency and coating strength. However, the calendar process may cause a decrease in the porosity (that is, the ink absorbability may be decreased), so it is necessary to set the conditions under which the decrease in the porosity is small.

  As roll temperature in the case of performing a calendar process, 30-150 degreeC is preferable and 40-100 degreeC is more preferable. Moreover, as a linear pressure between rolls at the time of a calendar process, 50-400 kg / cm is preferable and 100-200 kg / cm is more preferable.

In the case of inkjet recording, the thickness of the ink receiving layer needs to have an absorption capacity sufficient to absorb all of the droplets, and therefore needs to be determined in relation to the porosity in the layer. For example, if the ink amount is 8 nL / mm ² and the porosity is 60%, a film having a layer thickness of about 15 μm or more is required. Considering this point, in the case of ink jet recording, the layer thickness of the ink receiving layer is preferably 10 to 50 μm.

The pore diameter of the ink receiving layer is preferably 0.005 to 0.030 μm, more preferably 0.01 to 0.025 μm in terms of median diameter.
The porosity and the median diameter of the pores can be measured using a mercury porosimeter (trade name: Bore Sizer 9320-PC2, manufactured by Shimadzu Corporation).

  Further, the ink receiving layer is preferably excellent in transparency, but as a guide, the haze value when the ink receiving layer is formed on a transparent film is preferably 30% or less, and 20% or less. It is more preferable. The haze value can be measured with a haze meter (HGM-2DP: manufactured by Suga Test Instruments Co., Ltd.).

Hereinafter, each component constituting the first liquid or the second liquid will be described in detail.
(Inorganic fine particles)
The first liquid is preferably configured using inorganic fine particles. Examples of the inorganic fine particles include silica fine particles such as gas phase method silica and hydrous silica fine particles, colloidal silica, titanium dioxide, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, mica, talc, calcium carbonate, magnesium carbonate, sulfuric acid. Calcium, boehmite, pseudo boehmite and the like can be mentioned. These can be used alone or in combination of two or more. These inorganic fine particles are preferably dispersed and used with a cationic resin.

  Among the inorganic fine particles, gas phase method silica is particularly preferable, and the gas phase method silica and the other inorganic fine particles can be used in combination. The amount of the vapor phase silica in the total mass of the inorganic fine particles when used in combination is preferably 90% by mass or more, and more preferably 95% by mass or more.

  Silica fine particles are generally roughly classified into wet method particles and dry method (gas phase method) particles according to the production method. In the wet method, a method in which activated silica is produced by acid decomposition of a silicate, which is appropriately polymerized and coagulated and precipitated to obtain hydrous silica is the mainstream. On the other hand, in the vapor phase method, a method by high-temperature vapor phase hydrolysis of silicon halide (flame hydrolysis method), a method in which silica sand and coke are heated and reduced by an arc in an electric furnace and oxidized with air. The method of obtaining anhydrous silica by the (arc method) is the mainstream, and the “gas phase method silica” means anhydrous silica fine particles obtained by the gas phase method.

Vapor phase silica is different from hydrous silica in terms of the density of silanol groups on the surface, the presence or absence of vacancies, etc., and exhibits different properties, but is suitable for forming a three-dimensional structure with a high porosity. The reason for this is not clear, but in the case of hydrous silica, the density of silanol groups on the fine particle surface is high at 5 to 8 / nm ² , and the silica fine particles tend to aggregate (aggregate) easily. In the case of the method silica, the density of silanol groups on the surface of the fine particles is 2 to 3 / nm ² , so that it is sparse soft agglomeration (flocculate), resulting in a structure with a high porosity. Is done.

  Vapor phase silica has a particularly large specific surface area, so it has high ink absorption and retention efficiency, and low refractive index, so it provides transparency to the ink receiving layer when dispersed to an appropriate particle size. And high color density and good color development can be obtained. The transparency of the receiving layer is important from the viewpoint of obtaining a high color density and good color developing gloss even when applied to uses such as photo glossy paper.

  The average primary particle size of the vapor phase silica is preferably 20 nm or less, more preferably 10 nm or less, and particularly preferably 3 to 10 nm. Vapor phase silica is easy to adhere to each other by hydrogen bonds with silanol groups, so that when the average primary particle size is 20 nm or less, a structure with a large porosity can be formed, and ink absorption characteristics are effectively improved. In addition, the transparency and surface gloss of the ink receiving layer can be enhanced. In addition, the vapor phase method silica may be used as primary particles or may be contained in a state where secondary particles are formed.

Vapor phase silica is preferably used in a dispersed state. Vapor phase silica can be dispersed by using a cationic resin as a dispersant (flocculation inhibitor) and can be used as a vapor phase silica dispersion. The cationic resin is not particularly limited, but a cationic polymer having primary to tertiary amino groups and salts thereof, and a quaternary ammonium base, such as examples of other mordant components described later, is preferable. It is also preferable to use a silane coupling agent as the dispersant. Specifically, a water-soluble or aqueous emulsion type or the like can be preferably used. For example, a dicyan cation resin represented by a dicyandiamide-formalin polycondensate, a polyamine cation resin represented by a dicyanamide-diethylenetriamine polycondensate, epichlorohydrin - dimethylamine addition polymers, dimethyldiallylammonium chloride -SO ₂ copolymer, diallylamine salt -SO ₂ copolymer, dimethyl diallyl ammonium chloride polymer, polymer of allylamine salt, dialkylaminoethyl (meth) acrylate quaternary Examples thereof include polycationic cation resins such as salt polymers and acrylamide-diallylamine salt copolymers.

Among these, gas phase method silica having a specific surface area of 200 m ² / g or more by BET method is preferable. By containing vapor-phase process silica, a porous structure can be obtained and the ink absorption performance can be improved. Further, when the specific surface area is 200 m ² / g or more, the ink absorbability is improved and the speed is increased. The dryness and ink bleeding are improved, and the image quality and print density can be increased.

  Here, the BET method is one of the powder surface area measurement methods by the vapor phase adsorption method, and is a method for obtaining the total surface area, that is, the specific surface area of a 1 g sample from the 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 Brunauer Emmett and Teller's 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. .

(Water-soluble resin)
The first liquid is configured using a water-soluble resin. Examples of water-soluble resins include polyvinyl alcohol (PVA), polyvinyl acetal, cellulose resins [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.], chitins, and chitosans. , Starch; polyethylene oxide (PEO) which is a resin having an ether bond, polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE); polyacrylamide (PAAM) which is a resin having an amide group or an amide bond, Examples thereof include polyvinyl pyrrolidone (PVP) and polyacrylates, maleic resins, alginates, and gelatins having a carboxyl group as a dissociable group. These can be used alone or in combination of two or more.

  Among the above, polyvinyl alcohol is preferable, and the polyvinyl alcohol and the other water-soluble resin can be used in combination. The amount of polyvinyl alcohol in the total mass of the water-soluble resin when used in combination is preferably 90% by mass or more, and more preferably 95% by mass or more.

  In addition to polyvinyl alcohol (PVA), the polyvinyl alcohol includes cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, and other polyvinyl alcohol derivatives. Polyvinyl alcohol can be used alone or in combination of two or more.

The polyvinyl alcohol (PVA) has a hydroxyl group in its structural unit, and this hydroxyl group and a silanol group on the surface of the silica fine particle form a hydrogen bond, and a three-dimensional network structure having secondary particles of the silica fine particle as a chain unit. Make it easier to form. It is considered that this can form a porous structure ink receiving layer having a high porosity by forming a three-dimensional network structure.
The ink receiving layer having a porous structure as described above can absorb ink rapidly by capillary action during ink jet recording, and can form dots with good roundness without ink bleeding.

  The content of the water-soluble resin (particularly polyvinyl alcohol) is to prevent a decrease in film strength due to an insufficient amount and cracking during drying, and an excessive amount makes it easy for the voids to be clogged by the resin, resulting in a void ratio. From the viewpoint of preventing a decrease in ink absorbency due to a decrease, the amount is preferably 9 to 40% by mass, and 12 to 33% by mass with respect to the total solid mass of the layer when the ink receiving layer is formed. More preferred.

  As a number average polymerization degree of the said polyvinyl alcohol (PVA), 1800 or more are preferable from a viewpoint of crack prevention, and 2000 or more are more preferable. From the viewpoint of transparency and the viscosity of the coating liquid for forming the ink receiving layer, PVA having a saponification degree of 88% or more is preferable, and PVA having a saponification degree of 95% or more is particularly preferable.

-Content ratio of inorganic fine particles and water-soluble resin-
The content ratio of the inorganic fine particles (i) to the water-soluble resin (p) [PB ratio (i: p); the mass of the inorganic fine particles relative to 1 part by mass of the water-soluble resin] has a great influence on the film structure when the layer is formed. give. That is, as the PB ratio increases, the porosity, pore volume, and surface area (per unit mass) increase. Specifically, as the PB ratio, it is possible to prevent a decrease in film strength due to the PB ratio being too large and cracking at the time of drying, and the PB ratio is too small so that the voids are easily blocked by the resin. From the viewpoint of preventing the ink absorbency from being lowered due to the decrease in the porosity, 1.5: 1 to 10: 1 is preferable.

  Since stress may be applied when the ink jet recording medium passes through the transport system of the ink jet printer, the ink receiving layer needs to have sufficient film strength. Further, when cutting into a sheet shape, the ink receiving layer needs to have sufficient film strength in order to prevent cracking or peeling of the ink receiving layer. From this viewpoint, the PB ratio is preferably 5: 1 or less, and preferably 2: 1 or more from the viewpoint of securing high-speed ink absorbability with an inkjet printer.

For example, a coating solution in which a vapor phase silica having an average primary particle size of 20 nm or less and a water-soluble resin are completely dispersed in an aqueous solution at a PB ratio of 2: 1 to 5: 1 is applied on a support, and the coating layer Is dried, a three-dimensional network structure is formed in which the secondary particles of silica fine particles are chain units, the average pore diameter is 30 nm or less, the porosity is 50% to 80%, and the pore specific volume is 0.5 ml / g. As described above, a translucent porous film having a specific surface area of 100 m ² / g or more can be easily formed.

(Crosslinking agent)
The crosslinking agent may be contained in the first liquid and further contained in the second liquid.
The crosslinking agent is capable of crosslinking the above water-soluble resin, and by containing the crosslinking agent, a porous layer cured by a crosslinking reaction between the crosslinking agent and the water-soluble resin can be formed.

Boron compounds are preferred for crosslinking the above water-soluble resins, particularly polyvinyl alcohol resins. Examples of the boron compound include borax, boric acid, borates (for example, orthoborate, InBO ₃ , ScBO ₃ , YBO ₃ , LaBO ₃ , Mg ₃ (BO ₃ ) ₂ , Co ₃ (BO ₃ ) ₂ , 2 Borate (eg, Mg ₂ B ₂ O ₅ , Co ₂ B ₂ O ₅ ), metaborate (eg, LiBO ₂ , Ca (BO ₂ ) ₂ , NaBO ₂ , KBO ₂ ), tetraborate (eg, Na _{2 B 4 O 7 · 10H 2} O), can be mentioned five borate _{(e.g., KB 5 O 8 · 4H 2} O, Ca 2 B 6 O 11 · 7H 2 O, CsB 5 O 5) or the like. Among them, Of these, borax, boric acid, and borate are preferable, and boric acid is particularly preferable in that a crosslinking reaction can be promptly caused.

  Moreover, the following compounds other than a boron compound can also be used. For example, aldehyde compounds such as formaldehyde, glyoxal and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1,3,5- Active halogen compounds such as triazine and 2,4-dichloro-6-S-triazine sodium salt; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N′-ethylenebis (vinylsulfonylacetamide) ), Active vinyl compounds such as 1,3,5-triacryloyl-hexahydro-S-triazine; N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin; melamine resins (for example, methylolmelamine, alkylated methylolmelamine) ;Epoxy resin;

Isocyanate compounds such as 1,6-hexamethylene diisocyanate; aziridine compounds described in US Pat. Nos. 3,017,280 and 2,983611; carboximide compounds described in US Pat. No. 3,100,704; glycerol triglycidyl Epoxy compounds such as ether; Ethyleneimino compounds such as 1,6-hexamethylene-N, N′-bisethyleneurea; Halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; 2,3-dihydroxy Dioxane compounds such as dioxane; Titanium lactate, aluminum sulfate, chromium alum, potassium alum, metal-containing compounds such as zirconyl acetate and chromium acetate, polyamine compounds such as tetraethylenepentamine, hydrazide compounds such as adipic acid dihydrazide It is a small molecule or polymer or the like containing an oxazoline group two or more. The above crosslinking agents may be used singly or in combination of two or more.

  The crosslinking agent may be added to the ink receiving layer coating liquid and / or the coating liquid for forming the adjacent layer of the ink receiving layer when the ink receiving layer coating liquid is applied, or may be previously crosslinked. A coating liquid containing an ink receiving layer is applied onto a support on which a coating liquid containing an agent is applied. A coating liquid containing an ink receiving layer containing or not containing a cross-linking agent is applied and dried, and then a second liquid (for example, a cross-linking agent). The crosslinking agent can be supplied to the ink receiving layer by overcoating the agent solution.

For example, the crosslinking agent can be suitably applied as follows. Here, a boron compound will be described as an example. That is, the ink receiving layer coating liquid for the ink receiving layer when (first liquid) is a layer obtained by crosslinking and curing the applied coating layer, the crosslinking curing coating layer even during dry coating of the coating layer before presenting a decreasing rate of drying is carried out by applying a second liquid, cited above in the coating layer, a boron compound is a crosslinking agent may be contained either in the first solution or second solution, You may make it contain in both these liquids. When the ink receiving layer is composed of two or more layers, two or more coating liquids can be applied in multiple layers, and the second liquid may be applied from the layer formed.

  1-50 mass% is preferable with respect to the mass of water-soluble resin, and, as for the usage-amount of a crosslinking agent, 5-40 mass% is more preferable.

(Surfactant)
The first liquid preferably contains a surfactant. As the surfactant, any of cationic, anionic, nonionic, amphoteric, fluorine and silicone surfactants can be used. These surfactants may be used alone or in combination of two or more.

  Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenyl ethers (for example, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyalkylene ether) Ethylene nonylphenyl ether), oxyethylene / oxypropylene block copolymer, sorbitan fatty acid esters (for example, sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, etc.), polyoxyethylene sorbitan fatty acid esters (for example, polyoxyethylene) Sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitant Oleate, etc.), polyoxyethylene sorbitol fatty acid esters (eg, polyoxyethylene sorbitol tetraoleate), glycerin fatty acid esters (eg, glycerol monooleate), polyoxyethylene glycerin fatty acid esters (polyoxymonostearate) Ethylene glycerol, monooleic acid polyoxyethylene glycerin, etc.), polyoxyethylene fatty acid esters (polyethylene glycol monolaurate, polyethylene glycol monooleate, etc.), polyoxyethylene alkylamine, acetylene glycols (eg, 2, 4, 7) , 9-tetramethyl-5-decyne-4,7-diol, and ethylene oxide adducts and propylene oxide adducts of the diols), and the like. Sharp emission alkyl ethers are preferable. The nonionic surfactant may be contained in the ink receiving layer coating solution.

  Examples of the amphoteric surfactant include amino acid type, carboxyammonium betaine type, sulfoammonium betaine type, ammonium sulfate betaine type, imidazolium betaine type, and the like, for example, US Pat. No. 3,843,368, Those described in JP-A-59-49535, JP-A-63-236546, JP-A-5-303205, JP-A-8-262742, and JP-A-10-282619 can be suitably used. As the amphoteric surfactant, an amino acid type amphoteric surfactant is preferable, and as the amino acid type amphoteric surfactant, as described in JP-A-5-303205, for example, an amino acid (glycine, glutamic acid, Histidine acid etc.) and N-aminoacyl acids and salts thereof into which long chain acyl groups have been introduced.

Examples of the anionic surfactant include fatty acid salts (for example, sodium stearate, potassium oleate), alkyl sulfate esters (for example, sodium lauryl sulfate, triethanolamine lauryl sulfate), and sulfonates (for example, sodium dodecylbenzenesulfonate). Alkyl sulfosuccinate (for example, sodium dioctyl sulfosuccinate), alkyl diphenyl ether disulfonate, alkyl phosphate, and the like.
Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, pyridinium salts, imidazolium salts, and the like.

  Examples of the fluorosurfactant include compounds derived via an intermediate having a perfluoroalkyl group using a method such as electrolytic fluorination, telomerization, or oligomerization. Examples thereof include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trialkyl ammonium salts, perfluoroalkyl group-containing oligomers, and perfluoroalkyl phosphate esters.

  The silicone surfactant is preferably a silicone oil modified with an organic group, and can have a structure in which a side chain of a siloxane structure is modified with an organic group, a structure in which both ends are modified, or a structure in which one end is modified. Examples of the organic group modification include amino modification, polyether modification, epoxy modification, carboxyl modification, carbinol modification, alkyl modification, aralkyl modification, phenol modification, and fluorine modification.

  The content of the surfactant in the ink receiving layer coating solution is preferably 0.001 to 2.0%, more preferably 0.01 to 1.0%.

  As described above, the ink jet recording medium produced by the method for producing an ink jet recording medium of the present invention is configured by providing at least one ink receiving layer on a support, and the ink receiving layer is composed of a metal compound and a water-soluble layer. The resin composition may further contain other mordant components and other components as necessary.

-Support-
As the support usable in the present invention, any of a transparent support made of a transparent material such as plastic and an opaque support made of an opaque material such as paper can be used. In particular, in order to take advantage of the transparency of the ink receiving layer, it is preferable to use a transparent support or a highly glossy opaque support. Further, a read-only optical disk such as a CD-ROM or DVD-ROM, a write-once optical disk such as a CD-R or DVD-R, or a rewritable optical disk can be used as a support, and an ink receiving layer can be provided on both sides of the label. .

The material that can be used for the transparent support is preferably a material that is transparent and can withstand radiant heat when used in an OHP or a backlight display. Examples of the material include polyesters such as polyethylene terephthalate (PET); polysulfone, polyphenylene oxide, polyimide, polycarbonate, polyamide and the like. Of these, polyesters are preferable, and polyethylene terephthalate is particularly preferable.
Although there is no restriction | limiting in particular as thickness of the said transparent support body, 50-200 micrometers is preferable at the point which is easy to handle.

  As the highly glossy opaque support, one having a glossiness of 40% or more on the surface on which the ink receiving layer is provided is preferable. The glossiness is a value determined according to the method described in JIS P-8142 (75-degree specular gloss test method for paper and paperboard). Specifically, the following supports are mentioned.

  For example, high gloss paper support such as art paper, coated paper, cast coated paper, baryta paper used for silver salt photographic support, etc .; polyesters such as polyethylene terephthalate (PET), nitrocellulose, cellulose acetate , Cellulose esters such as cellulose acetate butyrate, and plastic films such as polysulfone, polyphenylene oxide, polyimide, polycarbonate, and polyamide are made opaque by adding a white pigment or the like (surface calendering may be applied). Glossy film; or a support in which a polyolefin coating layer containing or not containing a white pigment is provided on the surface of a highly glossy film containing the various paper supports, the transparent support or the white pigment. Etc. A white pigment-containing foamed polyester film (for example, foamed PET containing polyolefin fine particles and forming voids by stretching) can also be suitably exemplified.

  Although there is no restriction | limiting in particular also about the thickness of the said opaque support body, 50-300 micrometers is preferable at the point of handleability.

  The surface of the support may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, etc. in order to improve wettability and adhesion.

Next, the base paper used for the paper support will be described in detail.
As the base paper, wood pulp is used as a main raw material, and paper is made using synthetic pulp such as polypropylene or synthetic fiber such as nylon or polyester in addition to wood pulp as necessary. As the wood pulp, any of LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, NUKP can be used, but it is preferable to use more LBKP, NBSP, LBSP, NDP, LDP with a lot of short fibers. preferable. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less. The pulp is preferably a chemical pulp (sulfate pulp or sulfite pulp) with few impurities, and a pulp having a whiteness improved by bleaching is also useful.

  In the base paper, sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength enhancing agents such as starch, polyacrylamide and polyvinyl alcohol, fluorescent whitening agents, polyethylene glycols A water retaining agent such as a dispersant, a softening agent such as a quaternary ammonium, and the like can be appropriately added.

The freeness of the pulp used for papermaking is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is a 24 mesh residual mass% and a 42 mesh residual as defined in JIS P-8207. 30 to 70% of the sum with the mass% of is preferable. In addition, it is preferable that the mass% of 4 mesh remainder is 20 mass% or less. The basis weight of the base paper is preferably 30 to 250 g, and particularly preferably 50 to 200 g. The thickness of the base paper is preferably 40 to 250 μm. The base paper can be given a high smoothness by calendering at the paper making stage or after paper making. The density of the base paper is generally 0.7 to 1.2 g / m ² (JIS P-8118). Furthermore, the base paper stiffness is preferably 20 to 200 g under the conditions specified in JIS P-8143.

  A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, a sizing agent similar to the size that can be added to the base paper can be used. The pH of the base paper is preferably 5 to 9 when measured by a hot water extraction method defined in JIS P-8113.

  The surfaces on both sides of the base paper can generally be coated with polyethylene. The polyethylene is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but other LLDPE, polypropylene and the like can also be used in part.

  In particular, the polyethylene layer on the side on which the ink receiving layer is formed is obtained by adding rutile or anatase type titanium oxide, fluorescent whitening agent, ultramarine to polyethylene, as is widely done in photographic paper. Those having improved whiteness and hue are preferred. Here, as a titanium oxide content, about 3-20 mass% is preferable with respect to polyethylene, and 4-13 mass% is more preferable. Although the thickness of a polyethylene layer does not have limitation in particular, 10-50 micrometers is suitable for front and back layers. Further, an undercoat layer can be provided on the polyethylene layer in order to provide adhesion to the ink receiving layer. As the undercoat layer, aqueous polyester, gelatin and PVA are preferable. Moreover, as thickness of this undercoat layer, 0.01-5 micrometers is preferable.

  Polyethylene-coated paper can be used as glossy paper, or when it is coated by melt-extruding polyethylene onto the surface of the base paper, a matte or silky surface that can be obtained with ordinary photographic printing paper by performing a so-called molding process. Can also be used.

Next, other mordant components and other components will be described in detail.
-Other mordant components-
In the present invention, in addition to the above-described metal compound, another mordant component can be further contained for the purpose of further improving the bleeding with time and the water resistance of the image.
Examples of the other mordant components include organic mordants such as cationic polymers (cationic mordants), and inorganic mordants such as water-soluble metal compounds. The cationic mordant is preferably a polymer mordant having a primary to tertiary amino group or a quaternary ammonium base as a cationic functional group, but a cationic non-polymer mordant can also be used.

  As the polymer mordant, a homopolymer of a monomer having a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base (a mordant monomer), or the mordant monomer and other monomers (non-mordant) Those obtained as copolymers or condensation polymers with mordant monomers) are preferred. Moreover, these polymer mordants can be used in any form of a water-soluble polymer or water-dispersible latex particles.

  Examples of the mordant monomer include trimethyl-p-vinylbenzylammonium chloride, trimethyl-m-vinylbenzylammonium chloride, triethyl-p-vinylbenzylammonium chloride, triethyl-m-vinylbenzylammonium chloride, N, N-dimethyl- N-ethyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N-methyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-Nn-propyl-Np-vinylbenzyl Ammonium chloride, N, N-dimethyl-Nn-octyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-Np-vinylbenzylammonium chloride, N, N-diethyl-N Benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N- (4-methyl) benzyl-Np-vinylbenzylammonium chloride, N, N-dimethyl-N-phenyl-Np-vinyl Benzylammonium chloride;

Trimethyl-p-vinylbenzylammonium bromide, trimethyl-m-vinylbenzylammonium bromide, trimethyl-p-vinylbenzylammonium sulfonate, trimethyl-m-vinylbenzylammonium sulfonate, trimethyl-p-vinylbenzylammonium acetate, trimethyl-m-vinyl Benzylammonium acetate, N, N, N-triethyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N, N-triethyl-N-2- (3-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium chloride, N, N-diethyl-N-methyl-N-2- (4-vinylphenyl) ethylammonium chloride Tate;

N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N- Methyl chloride, ethyl chloride, methyl bromide of dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide , Quaternized products of ethyl bromide, methyl iodide or ethyl iodide, or sulfonates, alkyl sulfonates, acetates or alkyl carboxylates substituted with their anions.

  Specific examples of the compound include monomethyl diallylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium chloride, triethyl-2- (methacryloyloxy) ethylammonium chloride, trimethyl-2- (acryloyloxy) ethylammonium chloride, Triethyl-2- (acryloyloxy) ethylammonium chloride, trimethyl-3- (methacryloyloxy) propylammonium chloride, triethyl-3- (methacryloyloxy) propylammonium chloride, trimethyl-2- (methacryloylamino) ethylammonium chloride, triethyl- 2- (methacryloylamino) ethylammonium chloride, trimethyl-2- (acryloylua) C) ethylammonium chloride, triethyl-2- (acryloylamino) ethylammonium chloride, trimethyl-3- (methacryloylamino) propylammonium chloride, triethyl-3- (methacryloylamino) propylammonium chloride, trimethyl-3- (acryloylamino) Propylammonium chloride, triethyl-3- (acryloylamino) propylammonium chloride;

N, N-dimethyl-N-ethyl-2- (methacryloyloxy) ethylammonium chloride, N, N-diethyl-N-methyl-2- (methacryloyloxy) ethylammonium chloride, N, N-dimethyl-N-ethyl- 3- (acryloylamino) propylammonium chloride, trimethyl-2- (methacryloyloxy) ethylammonium bromide, trimethyl-3- (acryloylamino) propylammonium bromide, trimethyl-2- (methacryloyloxy) ethylammonium sulfonate, trimethyl-3- And (acryloylamino) propylammonium acetate. In addition, examples of copolymerizable monomers include N-vinylimidazole and N-vinyl-2-methylimidazole. In addition, a polymerization unit such as N-vinylacetamide, N-vinylformamide or the like, which is converted into a vinylamine unit by hydrolysis after polymerization, and a salt thereof can be used.

  The non-mordant monomer does not contain a basic or cationic moiety such as a primary to tertiary amino group and a salt thereof, or a quaternary ammonium base, and does not interact with a dye in an inkjet ink. Or a monomer having a substantially small interaction. For example, (meth) acrylic acid alkyl ester; (meth) acrylic acid cycloalkyl ester such as cyclohexyl (meth) acrylic acid; (meth) acrylic acid aryl ester such as phenyl (meth) acrylate; benzyl (meth) acrylic acid Aralkyl esters of styrene; vinyl aromatics such as styrene, vinyl toluene and α-methyl styrene; vinyl esters such as vinyl acetate, vinyl propionate and vinyl versatate; allyl esters such as allyl acetate; vinylidene chloride, vinyl chloride, etc. Halogen-containing monomers, vinyl cyanides such as (meth) acrylonitrile, olefins such as ethylene and propylene, and the like.

  The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl moiety, specifically, for example, methyl (meth) acrylate or ethyl (meth) acrylate. Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, (meth) Examples include octyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like. Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and hydroxyethyl methacrylate are preferable. The non-mordant monomer can also be used alone or in combination of two or more.

  Further, as the polymer mordant, polydiallyldimethylammonium chloride, polymethacryloyloxyethyl-β-hydroxyethyldimethylammonium chloride, polyethyleneimine, polyallylamine and a modified product thereof, polyallylamine hydrochloride, polyamide-polyamine resin, cationized starch, Dicyandiamide formalin condensate, dimethyl-2-hydroxypropylammonium salt polymer, polyamidine, polyvinylamine, cationic polyurethane resin described in JP-A-10-86505, and the like are also preferred.

  The modified polyallylamine is obtained by adding 2 to 50 mol% of acrylonitrile, chloromethylstyrene, TEMPO, epoxy hexane, sorbic acid or the like to polyallylamine, preferably 5 to 5 of acrylonitrile, chloromethylstyrene, and TEMPO. It is a 10 mol% adduct, and 5 to 10 mol% TEMPO adduct of polyallylamine is particularly preferable from the viewpoint of exhibiting an effect of preventing ozone fading.

  The molecular weight of the mordant is preferably 2000 to 300000 in terms of weight average molecular weight. When the molecular weight is within the above range, water resistance and aging resistance can be improved.

-Other components-
Further, the ink receiving layer contains the following components as required.
For the purpose of suppressing deterioration of the coloring material, various kinds of ultraviolet absorbers, surfactants, antioxidants, and anti-fading agents such as singlet oxygen quenchers may be included.
Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives, and the like. For example, α-cyano-phenyl cinnamate butyl, o-benzotriazole phenol, o-benzotriazole-p-chlorophenol, o-benzotriazole-2,4-di-t-butylphenol, o-benzotriazole-2,4 -Di-t-octylphenol etc. are mentioned. A hindered phenol compound can also be used as an ultraviolet absorber, and specifically, a phenol derivative in which at least one of 2-position or 6-position is substituted with a branched alkyl group is preferable.

  Moreover, a benzotriazole type ultraviolet absorber, a salicylic acid type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, an oxalic acid anilide type ultraviolet absorber, etc. can be used. For example, JP-A-47-10537, 58-111942, 58-21284, 59-19945, 59-46646, 59-109055, 63-53544. No. 36, Japanese Patent Publication No. 36-10466, No. 42-26187, No. 48-30492, No. 48-31255, No. 48-41572, No. 48-54965, No. 50-10726. No. 2,719,086, US Pat. No. 3,707,375, US Pat. No. 3,754,919, US Pat. No. 4,220,711, and the like. .

  A fluorescent brightening agent can also be used as an ultraviolet absorber, and examples thereof include a coumarin fluorescent brightening agent. Specifically, it is described in Japanese Patent Publication Nos. 45-4699 and 54-5324.

  Examples of the antioxidant include European Patent Publication No. 223739, Publication No. 309401, Publication No. 309402, Publication No. 310551, Publication No. 310552, Publication No. 4594416, Publication of German Patent No. 3435443, JP-A-54-48535, JP-A-60-107384, JP-A-60-107383, JP-A-60-125470, JP-A-60-125471, JP-A-60-125472, JP-A-60-287485. 60-287486, 60-287487, 60-287488, 61-160287, 61-185483, 61-2111079, 62-146678, 62-146680, 62-146679, 62-282885, JP same 62-262047, JP-same 63-051174, JP-same 63-89877, JP-same 63-88380, JP-same 66-88381, JP-same 63-113536, JP-

JP-A-63-163351, JP-A-63-203372, JP-A-63-224989, JP-A-63-251282, JP-A-63-267594, JP-A-63-182484, JP-A-1-239282, JP-A-2-262654, JP-A-2-71262, JP-A-3-121449, JP-A-4-29185, JP-A-4-291684, JP-A-5-61166, JP-A-5-119449, 5-188687, 5-188686, 5-110490, 5-110437, 5-170361, JP 48-43295, 48-33212, Examples thereof include those described in U.S. Pat. Nos. 4,814,262 and 4,980,275.

  Specifically, 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2-dihydroquinoline 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2,3 4, -tetrahydroquinoline, nickel cyclohexane acid, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2-ethylhexane, 2-methyl-4-methoxy-diphenylamine, Examples include 1-methyl-2-phenylindole.

  These anti-fading agents may be used alone or in combination of two or more. The anti-fading agent may be water-solubilized, dispersed, emulsified, or included in microcapsules. The addition amount of the anti-fading agent is preferably 0.01 to 10% by mass of the ink receiving layer coating solution.

  The ink receiving layer may contain various inorganic salts and acids, alkalis and the like as pH adjusting agents for the purpose of enhancing the dispersibility of the inorganic fine particles. Furthermore, for the purpose of suppressing surface frictional charge or peeling charge, the metal oxide fine particles having electronic conductivity may contain various matting agents for the purpose of reducing the surface frictional characteristics.

<Inkjet recording medium>
The ink jet recording medium of the present invention is an ink jet recording medium obtained by the method for producing an ink jet recording medium of the present invention, wherein all kinds of metal compounds in the ink receiving layer are more distributed as they are separated from the support. It is characterized by being.
According to a specific expression, the ink jet recording medium of the present invention is an ink jet recording medium obtained by a method for producing an ink jet recording medium, and the concentration ratio of all kinds of metal compounds in the ink receiving layer satisfies the following formula. It is characterized by that.
0.8 <C1 / C2 <1.0
However, C1 and C2 respectively represent the relative concentrations of the metal compounds in the layer in contact with the support and the layer not in contact when the ink receiving layer is divided into two equal parts in a cross section parallel to the support.

The ink jet recording medium of the present invention can be produced by the method for producing an ink jet recording medium of the present invention, and the contents of the first metal compound in the first liquid and the second metal compound in the second liquid are determined. By adjusting, all kinds of metal compounds in the ink receiving layer can be distributed more as they are separated from the support. Furthermore, by setting the C1 / C2 within the above range, there is no aggregation of the dye on the surface of the ink receiving layer, which is particularly effective in terms of suppressing bronzing.
The C1 / C2 measurement can be performed by TOF-SIMS measurement of the cross section of the ink receiving layer.

  In the present invention, the ink receiving layer may contain an acid. By adding an acid, the surface pH of the ink receiving layer is adjusted to 3-6, preferably 3-5. This is preferable because yellowing resistance of the white background portion is improved. The surface pH is measured by the A method (coating method) of the surface pH measurement determined by the Japan Paper Pulp Technology Association (J.TAPPI). For example, the measurement can be performed by using a paper PH measurement set “Type MPC” manufactured by Kyoritsu Riken Co., Ltd. corresponding to the method A.

Specific examples of acids include formic acid, acetic acid, glycolic acid, oxalic acid, propionic acid, malonic acid, succinic acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, isophthalic acid , Glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, salicylic acid, salicylic acid metal salts (Zn, Al, Ca, Mg, etc.), methanesulfonic acid, itaconic acid, benzenesulfonic acid, toluenesulfonic acid, trifluoromethanesulfone Acid, styrenesulfonic acid, trifluoroacetic acid, barbituric acid, acrylic acid, methacrylic acid, cinnamic acid, 4-hydroxybenzoic acid, aminobenzoic acid, naphthalenedisulfonic acid, hydroxybenzenesulfonic acid, toluenesulfinic acid, benzenesulfinic acid, Sulfanilic acid, sulfamic acid, α-le Examples include ricinic acid, β-resorcinic acid, γ-resorcinic acid, gallic acid, phloroglicin, sulfosalicylic acid, ascorbic acid, erythorbic acid, bisphenolic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid, boronic acid, etc. It is done. The amount of these acids added may be determined so that the surface pH of the ink receiving layer is 3-6.
The above acids can be metal salts (eg sodium, potassium, calcium, cesium, zinc, copper, iron, aluminum, zirconium, lanthanum, yttrium, magnesium, strontium, cerium, etc.) or amine salts (eg ammonia, triethylamine, tri Butylamine, piperazine, 2-methylpiperazine, polyallylamine, etc.).

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the examples, an inkjet recording sheet is prepared as an example of an inkjet recording medium, and “parts” and “%” in the examples represent mass standards unless otherwise specified.

[Example 1]
(Production of support)
50 parts of LBKP made of acacia and 50 parts of LBKP made of aspen were beaten to 300 ml of Canadian freeness by a disc refiner to prepare a pulp slurry.

  Next, the pulp slurry obtained above was charged with 1.3% cationic starch (CATO 304L manufactured by NSC Japan), 0.15% anionic polyacrylamide (polyaclon ST-13 manufactured by Seiko Chemical Co., Ltd.), and alkyl ketene dimer. (Arakawa Chemical Size Pine K) 0.29%, epoxidized behenamide 0.29%, polyamide polyamine epichlorohydrin (Arakawa Chemical Co., Ltd .: Arafix 100) 0.32%, then added antifoaming agent 0.12% was added.

In the process of making the pulp slurry prepared as described above with a long paper machine and pressing the felt surface of the web against the drum dryer cylinder through the dryer canvas for drying, the tensile force of the dryer canvas is 1.6 kg / After drying at a setting of cm, 1 g / m ² of polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: KL-118) was applied to both sides of the base paper with a size press and dried to perform calendar treatment. The base paper was made with a basis weight of 166 g / m ² to obtain a base paper (base paper) having a thickness of 160 μm.

After the corona discharge treatment was performed on the wire surface (back surface) side of the obtained base paper, high-density polyethylene was coated to a thickness of 25 μm using a melt extruder, and a thermoplastic resin layer comprising a mat surface was formed. (Hereinafter, this thermoplastic resin layer surface is referred to as “back surface”). The thermoplastic resin layer on the back side is further subjected to corona discharge treatment, and then, as an antistatic agent, aluminum oxide (“Alumina Sol 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (manufactured by Nissan Chemical Industries, Ltd.) Of “Snowtex O”) was dispersed in water at a mass ratio of 1: 2 so that the dry mass was 0.2 g / m ² .

  Further, after the corona discharge treatment is performed on the felt surface (surface) side where the thermoplastic resin layer is not provided, 10% of anatase-type titanium dioxide and 0.3% of ultramarine manufactured by Tokyo Ink Co., Ltd. are contained. The amount of the fluorescent whitening agent “Whitefloor PSN conc” manufactured by Nippon Chemical Industry Co., Ltd. was adjusted to 0.08%. A low density polyethylene of MFR (melt flow rate) 3.8 is extruded to a thickness of 25 μm by using a melt extruder, and a high gloss thermoplastic resin layer is formed on the surface side of the base paper (hereinafter referred to as this The highly glossy surface is referred to as the “front surface”), and a support was prepared. This support was made into a long roll body with a width of 1.5 m and a winding length of 3000 m.

-Preparation of coating liquid A (first liquid) for ink receiving layer-
(1) Gas phase method silica fine particles having the following composition, (2) ion-exchanged water, (3) “Charol DC-902P”, and (4) “ZA-30” are mixed, and a bead mill (for example, KD -P (manufactured by Shinmaru Enterprises Co., Ltd.) was used, and the dispersion was heated to 45 ° C. and held for 20 hours, after which (5) boric acid and (6) polyvinyl alcohol were added. The solution, (7) “Superflex 600B”, (8) polyoxyethylene lauryl ether, and (9) ethanol were added at 30 ° C. to prepare an ink receiving layer coating solution A (first solution).

<Composition of coating liquid A for ink receiving layer>
(1) Gas phase method silica fine particles (inorganic fine particles) 10.0 parts (AEROSIL300SF75, manufactured by Nippon Aerosil Co., Ltd.)
(2) Ion-exchanged water 64.8 parts (3) "Charol DC-902P" (51.5% aqueous solution) 0.87 parts (dispersant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(4) “ZA-30” (zirconium acetate) 0.54 parts (5) boric acid (crosslinking agent) 0.37 parts (6) polyvinyl alcohol (water-soluble resin) solution 29.4 parts (composition of solution) “PVA235” manufactured by Kuraray Co., Ltd., saponification degree 88%, polymerization degree 3500) 2.03 parts polyoxyethylene lauryl ether (surfactant) 0.03 parts The following compound 1 0.06 parts triethylene glycol monobutyl ether 0 .68 parts (Butizenol 20P, manufactured by Kyowa Hakko)
Ion-exchanged water 26.6 parts (7) "Superflex 600B" 1.24 parts (Daiichi Kogyo Seiyaku Co., Ltd.)
(8) 0.49 part of polyoxyethylene lauryl ether (surfactant) (“Emulgen 109P” (10% aqueous solution), HLB value 13.6 parts, manufactured by Kao Corporation)
(9) 2.49 parts of ethanol

-Preparation of inkjet recording sheet-
After the corona discharge treatment is applied to the front surface of the support, a 5-fold diluted aqueous solution of polyaluminum chloride (polyaluminum chloride is alpha-in 83) is added to the first solution that is flowed to a coating amount of 173 ml / m ^2. (Manufactured by Daimei Chemical Co., Ltd.) In-line coating was performed at a rate of 10.8 ml / m ² and dried with a hot air dryer at 80 ° C. (wind speed 3 to 8 m / sec) until the solid content concentration of the coating layer reached 20%. This coating layer exhibited a constant rate of drying during this period, and was dipped in the basic solution B (second solution) having the following composition for 3 seconds before exhibiting reduced-rate drying. 13 g / m ² was adhered to the substrate, and further dried at 80 ° C. for 10 minutes (step (B), curing step), whereby the ink jet ink of Example 1 provided with an ink receiving layer having a dry film thickness of 32 μm. A recording medium was produced.

<Composition of basic solution B>
(1) Boric acid 0.65 parts (2) Zirconium ammonium carbonate 2.5 parts (Zircosol AC-7 (28% aqueous solution), manufactured by Daiichi Rare Element Chemical Co., Ltd.)
(3) Ammonium carbonate (first grade; manufactured by Kanto Chemical Co., Inc.) 3.5 parts (4) Ion-exchanged water 63.3 parts (5) Polyoxyethylene lauryl ether (surfactant) 30.0 parts (Kao Corporation ), Emulgen 109P (2% aqueous solution), HLB value 13.6)

[ Comparative Example 4 ]
An inkjet recording medium of Comparative Example 4 was produced in the same manner as in Example 1 except that the 5-fold diluted polyaluminum chloride aqueous solution was not applied in-line in Example 1.

[ Comparative Example 5 ]
An inkjet recording medium of Comparative Example 5 was produced in the same manner as in Example 1 except that “ZA-30” was removed from the first liquid in Example 1.

[ Comparative Example 6 ]
In Comparative Example 4 , Comparative Example 6 was performed in the same manner as Comparative Example 4 except that “ZA-30” was excluded from the first solution and 0.27 part of magnesium chloride.6H ₂ O and 0.27 part of aluminum sulfate were added. An ink jet recording medium was prepared.

[Comparative Example 1]
In the comparative example 6 , the inkjet recording medium of the comparative example 1 was produced like the comparative example 4 except having changed the 2nd liquid into the following composition.
<Composition of the second liquid>
(1) Boric acid 0.65 parts (2) Polyallylamine 20% aqueous solution 3.0 parts (PAA-03, manufactured by Nittobo Co., Ltd .; mordant)
(3) 1.8 parts of p-toluenesulfonic acid (manufactured by Gangnam Chemical Co., Ltd.)
(4) Ammonium chloride (manufactured by Central Glass Co., Ltd.) 0.1 part (5) ion-exchanged water 63.3 parts (6) polyoxyethylene lauryl ether (surfactant) 10.0 parts (manufactured by Kao Corporation) "Emulgen 109P" (2% aqueous solution), HLB value 13.6)
(7) Fluorosurfactant (10% aqueous solution) 0.2 part (Megafac F1405, manufactured by Dainippon Ink & Chemicals, Inc.)

[Comparative Example 2]
An inkjet recording medium of Comparative Example 2 was produced in the same manner as Comparative Example 1 except that aluminum sulfate was removed from the first liquid of Comparative Example 1.

[Comparative Example 3]
An ink jet recording medium of Comparative Example 3 was produced in the same manner as in Example 1 except that “ZA-30” was removed from the first liquid and zircozol AC-7 was removed from the second liquid.

[Evaluation]
The following evaluation was performed about each of the inkjet recording medium of the Example obtained from the above, and the inkjet recording medium of a comparative example . The evaluation results are shown in Table 1 below.
(1) Evaluation of color density For each ink jet recording medium, a solid image of yellow, magenta, cyan, and black was printed on each ink jet recording medium using an ink jet printer (manufactured by Seiko Epson Corporation, “PM970C”) at 23 ° C. Then, each color density of each ink jet recording medium was measured with a reflection density meter (X-rite 938, manufactured by X-Rite Co., Ltd.), and a black density with a large color density change was displayed. It is shown in 1.

(2) Evaluation of glossiness A black solid image was printed on each ink jet recording medium using an ink jet printer (manufactured by Seiko Epson Corporation, “PM-970C”). Then, using a digital variable angle gloss meter (Suga Test Instruments Co., Ltd. UGV-5D measuring hole 8mm), the glossiness of the black solid image portion is measured at an incident angle of 45 degrees, a light receiving angle of 42 degrees, 45 degrees, and 48 degrees. The glossiness was calculated by the following formula. When the glossiness is less than 0.05, the diffuse reflection light component from the surface of the recording sheet is reduced, so that a preferable glossiness similar to a silver salt photograph can be obtained.
Glossiness = ((42 degree gloss + 48 degree gloss) / 2) / (45 degree gloss)

(3) Evaluation of blur A grid-like linear pattern (line) in which magenta ink and black ink are arranged adjacent to each other on each inkjet recording medium using an inkjet printer (manufactured by Seiko Epson Corporation, “PM-970C”). Width 0.28 mm) was printed. Immediately after printing, the printed inkjet recording medium was inserted into a transparent PP file, and stored for 3 days in an environment of 35 ° C. and a relative humidity of 80%. Thereafter, the width of the black line of the linear pattern was measured, and the bleeding (%) with time was calculated from the measured value and the width of the black line immediately after printing, which was separately obtained, by the following formula.
Bleeding with time (%) = (width of black line of linear pattern stored at 35 ° C. and 80% for 3 days) / (width of black line immediately after printing) × 100

(4) Evaluation of bronzing About each ink jet recording sheet, a dark blue solid image was printed using an ink jet printer (manufactured by Seiko Epson Corporation, “PM-970C”), and bronzing occurred after being left for one day. The degree was evaluated visually. Those that did not occur were marked as ◯, and those that occurred were marked as x.

From Table 1, the ink jet recording media of the examples obtained the results satisfying all of the color density, glossiness, blurring, and bronzing at the same time, whereas the ink jet recording media of the comparative example had the color density, glossiness. , Rainbow, and bronzing were inferior.

Claims (9)

In the method for producing an ink jet recording medium having an ink receiving layer on a support, the ink receiving layer is formed by at least the following steps (A) and (B). A method for manufacturing a recording medium.
Step (A): A step of forming a coating layer by applying a first liquid containing a water-soluble resin, a crosslinking agent, and two kinds of first metal compounds selected from a zirconium compound and an aluminum compound on a support. Step (B): A second liquid containing a second metal compound selected from a zirconium compound is applied to the coating layer before the coating layer is in the course of drying and before the coating layer exhibits reduced drying. And a step of crosslinking and curing the coating layer   The method for producing an ink jet recording medium according to claim 1, wherein the second liquid further contains a basic compound.   The method for producing an ink jet recording medium according to claim 1, wherein the first liquid further contains inorganic fine particles.   The method for producing an ink jet recording medium according to any one of claims 1 to 3, wherein the first liquid or the second liquid further contains a surfactant. Wherein the basic compound, method of manufacturing an ink jet recording medium according to any one of claims 2 to 4, characterized in that a weak acid of the ammonium salt. The method for producing an ink jet recording medium according to any one of claims 1 to 5 , wherein the water-soluble resin is polyvinyl alcohol. The method for producing an ink jet recording medium according to any one of claims 1 to 6 , wherein the crosslinking agent is a boron compound. The inkjet recording medium according to any one of claims 1 to 7 , wherein the pH of the first liquid is 6.0 or less, and the pH of the second liquid is 7.1 or more. Method. 9. The inkjet according to claim 1, wherein the content of the second metal compound in the second liquid is 0.1 to 0.8 mass% with respect to the total mass of the second liquid. A method for manufacturing a recording medium.