JP2009083299A - Method for manufacturing inkjet recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an inkjet recording medium capable of obtaining high printing density and suppressing coating defects. <P>SOLUTION: The method for manufacturing the inkjet recording medium includes a process of applying: at least a coating liquid A containing a vapor-phase-process silica and a water-soluble binder; a coating liquid B containing a pseudo boehmite alumina hydrate, in which the content of water-soluble binder with respect to the content of the pseudo boehmite alumina hydrate and the content of a crosslinking agent with respect to the content of the pseudo boehmite alumina hydrate are respectively less than 3 mass%; and a coating liquid C containing the crosslinking agent, in this order on a support body from the support body side to form an ink receiving layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an inkjet recording medium.

  With the rapid development of the information technology industry in recent years, various information processing systems have been developed, and recording methods and recording apparatuses suitable for each information processing system have been put into practical use. Among these, the ink jet recording method is widely used because it can record on various recording materials, the hardware (device) is relatively inexpensive and compact, and has excellent quietness. ing. In the recording using the ink jet recording method, it has become possible to obtain a so-called photographic-like high quality recorded matter.

  In general, recording materials for ink-jet recording are (1) fast-drying (high ink absorption speed), (2) proper and uniform dot diameter (no bleeding), and (3) granular (4) High roundness of dots, (5) High color density, (6) High saturation (no dullness), (7) Water resistance of image area (8) High whiteness, (9) High storage stability (no yellowing coloring or bleeding of images after long-term storage), (10) It is required to have properties such as being hard to deform and having good dimensional stability (low curl) and (11) good hard running performance.

In view of the above, in recent years, an ink jet recording medium (ink jet recording material) in which an ink receiving layer has a porous structure has been put into practical use and various studies have been made.
For example, as a technique for suppressing coating defects and obtaining good ink absorptivity, a first step of applying a first coating liquid containing a crosslinking agent on a substrate, and then in the first step A technique for forming an ink receiving layer in a second step in which a second coating liquid containing inorganic fine particles and a binder is applied and crosslinked and cured at the same time as application or before the first coating liquid is dried and solidified. It is known (see, for example, Patent Document 1).

  Further, as a technique for increasing ink absorbability, glossiness, and print density, at least two ink-receiving layers are provided on a water-resistant support, and the ink-receiving layer close to the water-resistant support is formed by vapor phase silica, boric acid. Alternatively, an ink receiving layer (A) containing borate and a polyvinyl alcohol having a polymerization degree of less than 3000 is used, and the ink receiving layer far from the water-resistant support is made of alumina or alumina hydrate, boric acid or borate, and a polymerization degree of 3000. A technique for using the above-described polyvinyl alcohol-containing ink receiving layer (B) is known (for example, see Patent Document 2).

In addition, as a technology that has a photo-like high gloss, excellent ink absorbability, color developability, and productivity, and has no discoloration around the printed portion, at least one of the ink receiving layers provided on the support is used. In an inkjet recording material containing inorganic fine particles having an average secondary particle diameter of 500 nm or less, a resin binder having an acetoacetyl group, and a compound having two or more terminal hydrazino groups, at least one of the ink receiving layers has a pKa value of 2. A technique containing an organic acid that is 5 to 5 is known (see, for example, Patent Document 3).
JP 2004-230599 A JP 2002-225423 A JP 2007-69593 A

However, it has been clarified that in a system in which the ink-receiving layer contains pseudo boehmite-like alumina hydrate, a water-soluble binder and a crosslinking agent, aggregation tends to occur and coating defects such as cracks are likely to occur. Therefore, it is not always possible to achieve both high printing density and suppression of coating defects only by the conventional technique.
The present invention has been made in view of the above, and an object of the present invention is to provide a method for producing an ink jet recording medium in which a high printing density is obtained and coating defects are suppressed, and an object thereof is to achieve the object.

Specific means for solving the above-described problems are as follows.
<1> A coating liquid A containing at least (A) gas phase method silica and a water-soluble binder and (B) pseudo-boehmite-like alumina hydrate on the support, and against the pseudo-boehmite-like alumina hydrate A coating solution B in which the content of the water-soluble binder and the content of the crosslinking agent relative to the pseudo boehmite-like alumina hydrate are both less than 3% by mass, and (C) the coating solution C containing the crosslinking agent are supported. This is a method for manufacturing an ink jet recording medium, which includes a step of forming an ink receiving layer by applying in this order from the body side.
<2> The method for producing an inkjet recording medium according to <1>, wherein an average primary particle diameter of the vapor phase silica and the pseudo boehmite-like alumina hydrate is 3 to 20 nm.

<3> The ink jet recording according to <1> or <2>, wherein the support is a base paper, and a surface of the formed ink receiving layer is calendered by a calender device having a mirror roll. It is a manufacturing method of a medium.
<4> The method for producing an inkjet recording medium according to <1> or <2>, wherein the support is a water-resistant support.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the inkjet recording medium with which the high printing density was obtained and the coating defect was suppressed can be provided.

Hereafter, the manufacturing method of the inkjet recording medium of this invention is demonstrated in detail.
The method for producing an inkjet recording medium of the present invention comprises, on a support, at least (A) a coating solution A containing vapor phase silica and a water-soluble binder, and (B) pseudoboehmite-like alumina hydrate, A coating liquid B in which the content of the water-soluble binder with respect to the pseudo boehmite-like alumina hydrate and the content of the crosslinking agent with respect to the pseudo-boehmite-like alumina hydrate are both less than 3% by mass, and (C) a crosslinking agent are included. Coating liquid C is applied in this order from the support side (that is, coating liquid A, coating liquid B, and coating liquid C as viewed from the support side) to form an ink receiving layer. It is comprised including the process to perform. The ink receiving layer may be formed by applying other coating liquid as required.

Pseudoboehmite-like alumina hydrate is a component that contributes to improving the printing density. However, in a system in which the ink-receiving layer contains pseudoboehmite-like alumina hydrate, a water-soluble binder, and a cross-linking agent, coagulation and increase in coating liquid are achieved. It became clear that viscosity was likely to occur and coating defects were likely to occur in the coating layer formed by coating the coating solution.
Therefore, by making the method for producing an ink jet recording medium according to the above-described configuration of the present invention, the contact between the pseudo boehmite-like alumina hydrate, the cross-linking agent, and the water-soluble binder is suppressed, so that the occurrence of coating defects is effectively suppressed. Is done. For this reason, it is possible to produce an ink jet recording medium in which a high printing density is obtained and coating defects are also suppressed.

<Preparation of coating solution>
In the present invention, the method for preparing the coating liquid A, the coating liquid B, and the coating liquid C is not particularly limited, and a known method of mixing and stirring each component contained in each coating liquid can be used.
From the viewpoint of more effectively suppressing coating defects, in preparing the coating liquid A or the coating liquid B, first, a fine particle dispersion (gas phase method silica dispersion or pseudoboehmite-like alumina hydrate dispersion) is prepared. In addition, a method of mixing the prepared fine particle dispersion and other components after that is preferable.
At this time, a form in which the fine particle dispersion and other components are kept warm at the same temperature and mixed while keeping the temperature is preferable. As specific temperature, in preparation of the coating liquid A, 15-45 degreeC is preferable and 20-40 degreeC is more preferable. In preparation of the coating liquid B, 40-70 degreeC is preferable and 45-60 degreeC is more preferable.

<Application>
In the present invention, the coating liquid A, the coating liquid B, and the coating liquid C may be applied by simultaneously applying the coating liquid A, the coating liquid B, and the coating liquid C, or the coating liquid A and the coating liquid C may be applied. It may be performed by sequentially applying the liquid B and the coating liquid C, or may be performed by combining simultaneous multilayer coating and sequential coating.
Here, the application can be performed by a known application method. Examples thereof include a slide bead method, a curtain method, an extrusion method, an air knife method, a roll coating method, and a Ked bar coating method.

The sequential coating is a method of coating one liquid at a time in the order of coating liquid A, coating liquid B, and coating liquid C, for example.
In the present invention, as a form in the case of using sequential coating, (1) a form in which coating liquid A, coating liquid B, and coating liquid C are applied one by one in the order, (2) coating liquid A and coating liquid B are simultaneously layered. Examples include a mode in which the coating liquid C is sequentially applied after coating, and a mode in which (3) the coating liquid A is sequentially coated and then the coating liquid B and the coating liquid C are simultaneously applied in multiple layers.
At the time of sequential application, the next coating solution may be applied before the coating solution already applied on the support (hereinafter also referred to as “lower layer coating solution”) is dried, or the lower layer side coating solution. After drying, the next coating solution may be applied. Further, for example, a “Wet-On-Wet method (WOW method)” described in paragraphs 0016 to 0037 of JP-A-2005-14593 may be used.

On the other hand, the simultaneous multilayer coating is a method in which at least two (preferably all coating solutions) of the coating solution A, the coating solution B, and the coating solution C are applied simultaneously without providing a drying step.
Among the above, from the viewpoint of suppressing mixing of each component in each coating liquid and from the viewpoint of production efficiency, simultaneous multilayer coating is preferable, and among these, simultaneous multilayer coating using a slide bead method, a curtain method, etc. is more preferable. .
In the simultaneous multi-layer coating, it is preferable to apply each coating solution while keeping the temperature warm. As temperature of each coating liquid at this time, 35-55 degreeC is preferable and 40-50 degreeC is more preferable.

<Dry>
The coating film (ink receiving layer) formed by the coating can be dried by a known method.
The drying temperature depends on the heat resistance of the support, but is preferably in the range of 10 to 100 ° C, more preferably 20 to 80 ° C.
In addition, after the application, after the ink receiving layer is sufficiently dried, the pore volume of the ink receiving layer can be increased by performing a heat treatment within a range that does not adversely affect the support, so that the ink absorbability is improved. Furthermore, the water resistance of the ink receiving layer can be improved. The temperature for the heat treatment depends on the heat resistance of the support, but is preferably 30 to 80 ° C, more preferably 40 to 60 ° C.

<Ink receiving layer>
In the method for producing an inkjet recording medium of the present invention, the ink receiving layer is formed on the support by laminating the coating liquid A, the coating liquid B, and the coating liquid C in this order from the support side.
The formed ink receiving layer clearly recognizes a laminated structure composed of at least three layers, such as a layer obtained from the coating liquid A, a layer obtained from the coating liquid B, and a layer obtained from the coating liquid C. It may be in a state where it can be formed, or it may be in a state where the interface between layers is mixed and the laminated structure cannot be clearly recognized.
The total thickness of the formed ink receiving layer is not particularly limited, but is preferably 20 to 60 μm and more preferably 30 to 50 μm from the viewpoint of ink absorbability.

  Hereinafter, each component in the ink receiving layer (that is, in the coating liquid A, the coating liquid B, and the coating liquid C) will be described, and then the support will be described.

<Pseudo boehmite-like alumina hydrate>
The coating liquid B in the present invention contains at least one pseudo boehmite-like alumina hydrate. The pseudo boehmite-like alumina hydrate may be contained in other coating liquids other than the coating liquid B as necessary.

The pseudo-boehmite-like alumina hydrate is represented by a constitutional formula of Al ₂ O ₃ .nH ₂ O (1 <n <3), and refers to an alumina hydrate when n is greater than 1 and less than 3.
Hereinafter, the pseudo boehmite-like alumina hydrate is also simply referred to as “alumina hydrate”.

The alumina hydrate may be crystalline or amorphous, and the shape thereof may be any one of an indeterminate shape, a spherical shape, a plate shape, etc., or a combination of a plurality. May be.
As an average primary particle diameter of the said alumina hydrate, 3-30 nm is preferable and 3-20 nm is more preferable. The aspect ratio of the alumina hydrate is preferably 2 or more.

  As the pre-alumina hydrate, usually, a secondary particle crystal of several thousand to several tens of thousands nm can be preferably used after being pulverized to about 50 to 300 nm by an ultrasonic wave, a high-pressure homogenizer, a counter collision type jet pulverizer or the like.

  For dispersion of the alumina hydrate of the present invention, an acid such as lactic acid, acetic acid, formic acid, nitric acid, hydrochloric acid, hydrobromic acid, aluminum chloride may be used.

In the present invention, the average primary particle diameter of the alumina hydrate is obtained by observing the diameter of a circle equal to the projected area of each of 100 particles existing in a certain area by electron microscope observation of the dispersed particles. be able to. In addition, you may use a commercial item manufacturer nominal value for an average primary particle diameter.
In the case of spindle-shaped particles, the average particle diameter is obtained by averaging the major axis and the minor axis. The average thickness of the plate-like alumina hydrate is obtained by observing the cut surface of the sheet coated with the alumina hydrate on the film, and the aspect ratio of the alumina hydrate is obtained as the ratio of the average particle diameter to the average thickness. be able to. The average secondary particle size of the alumina hydrate can be measured with a laser diffraction / scattering particle size distribution analyzer using a dilute dispersion.
In addition, the average primary particle diameter and average secondary particle diameter of the vapor phase method silica fine particles to be described later can also be determined by the same method as for alumina hydrate.

  The average pore radius of the alumina hydrate is preferably 1 to 10 nm, and particularly preferably 2 to 7 nm, from the viewpoint of improving the ink absorption rate of the ink receiving layer. When the average pore radius is within the above range, the ink absorptivity is good, the fixing of the dye in the ink is good, and the occurrence of image bleeding can be avoided.

The pore volume of the alumina hydrate is preferably in the range of 0.1 to 0.8 ml / g, particularly in the range of 0.4 to 0.6 ml / g from the viewpoint of improving the ink absorption capacity of the ink receiving layer. A range is preferred. When the pore volume of the ink receiving layer is within the above range, it is possible to avoid the occurrence of cracks and powder falling in the ink receiving layer, and the ink absorption is improved. The pore volume at a pore radius of 2 nm to 10 nm is preferably 0.1 ml / g or more. Within this range, the adsorption of the dye in the ink becomes good. Further, the solvent absorption amount per unit area of the ink receiving layer is preferably 5 ml / m ² or more, and particularly preferably 10 ml / m ² or more. When the solvent absorption amount per unit area is within the above range, it is possible to prevent ink overflow particularly when multicolor printing is performed.

In order for the alumina hydrate to sufficiently absorb and fix the dye in the ink, the BET specific surface area of the alumina hydrate is preferably in the range of 70 to 300 m ² / g. When the BET specific surface area is within the above range, the alumina hydrate can be dispersed well, the pore size distribution is not deviated, the fixing efficiency of the dye in the ink is improved, and image bleeding can be avoided.

In order to increase the concentration of the alumina hydrate dispersion, the number of surface hydroxyl groups of the alumina hydrate is preferably 10 ²⁰ / g or more. When the number of surface hydroxyl groups is small, the alumina hydrate tends to aggregate and it is difficult to increase the concentration of the dispersion.

  The alumina hydrate can be produced by a known method such as hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali, hydrolysis of aluminate. The particle size, pore size, pore volume, specific surface area, number of surface hydroxyl groups, etc. of the alumina hydrate can be controlled by the precipitation temperature, aging time, solution pH, solution concentration, coexisting salts and the like.

  For example, JP-A-57-88074, JP-A-62-56321, JP-A-4-275717, JP-A-6-64918, JP-A-7-10535, JP-A-7-267633, U.S. Pat. No. 2,656,321. No., Am. Ceramic Soc. Bull. , 54, 289 (1975), etc. disclose a method for hydrolyzing aluminum alkoxide. These aluminum alkoxides include isopropoxide, propoxide, 2-butoxide and the like. By this method, a highly pure alumina hydrate can be obtained.

  In addition, as a method for obtaining alumina hydrate, as disclosed in JP-A Nos. 54-116398, 55-23034, 55-27824, 56-120508, etc., aluminum Generally, a method for obtaining an inorganic salt or a hydrate thereof as a raw material. Examples of these inorganic salts include inorganic salts such as aluminum chloride, aluminum nitrate, aluminum sulfate, polyaluminum chloride, ammonium alum, sodium aluminate, potassium aluminate, aluminum hydroxide, and hydrates of these inorganic salts. Etc.

  Specifically, for example, an alumina hydrate is obtained by a neutralization reaction between an aqueous solution of an acidic aluminum salt such as aluminum sulfate, aluminum nitrate, or aluminum chloride and a basic aqueous solution such as sodium aluminate, sodium hydroxide, or aqueous ammonia. Can be manufactured. In this case, it is common to mix within a range where the amount of alumina hydrate produced in the liquid does not exceed 5% by mass, and to react under conditions of pH 6 to 10 and temperature 20 to 100 ° C. Further, as described in JP-A-56-120508, a method for growing alumina hydrate crystals by alternately changing the pH to the acid side and the base side, aluminum described in JP-B-4-33728 It can also be produced by a method of rehydrating alumina by mixing alumina hydrate obtained from the inorganic salt and alumina obtained by the Bayer method.

Further, from the viewpoint of print density, the total amount of the pseudo boehmite alumina hydrate in the ink-receiving layer is preferably from 5~35g / ^{m 2,} and more preferably 10 to 25 g / ^{m 2.}
Further, from the viewpoint of coexistence of crack suppression and ink absorbency improvement, the content of the pseudo boehmite-like alumina hydrate in the coating liquid B is 80 to 100% by mass with respect to the total solid content of the coating liquid B. Preferably, 90-100 mass% is more preferable.

<Gas phase method silica>
The coating liquid A in the present invention contains at least one gas phase method silica. The gas phase method silica may be contained in other coating liquids other than the coating liquid A as necessary.
Synthetic silica is classified into a wet method and a gas phase method. In general, silica fine particles often refer to wet process silica. Wet silicas include (1) silica sol obtained through metathesis with sodium silicate acid and ion exchange resin layer, or (2) colloidal silica obtained by heating and aging this silica sol, and (3) gelation of silica sol. Then, by changing the production conditions, silica gel in which primary particles of several to 10 μm are converted into three-dimensional secondary particles having siloxane bonds, and (4) silica sol, sodium silicate, sodium aluminate, etc. There are synthetic silicic acid compounds mainly composed of silicic acid such as those obtained by heating.

The vapor-phase process silica used in the present invention is also called a dry process, and is generally made by a flame hydrolysis method. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane can be used alone or silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state. Vapor phase method silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd., and can be obtained.
The average primary particle diameter of the vapor phase silica in the present invention is preferably 3 to 50 nm, more preferably 3 to 20 nm, from the viewpoint of obtaining higher gloss.
In general, the vapor phase silica is agglomerated to form secondary particles having appropriate voids, preferably using vapor phase silica having an average primary particle diameter of 3 to 50 nm, preferably 500 nm or less, preferably Is preferably pulverized and dispersed with ultrasonic waves, a high-pressure homogenizer, a counter-impact type jet pulverizer or the like until it becomes secondary particles of 180 to 400 nm, because of its good gloss and ink absorbability.

  From the viewpoint of further improving the printing density, it is preferable that both of the average primary particle diameter of the vapor-phase process silica and the average primary particle diameter of the pseudo boehmite-like alumina hydrate are 3 to 20 nm. 7 to 12 nm is particularly preferable.

Further, from the viewpoint of ink absorption, the total amount of fumed silica in the ink receiving layer is preferably ^{3~15g / m 2, 5~11g / m} 2 is more preferable.
Further, from the viewpoint of achieving both improvement in ink absorbency and suppression of cracks, the content of the vapor phase silica in the coating liquid A is preferably 70 to 90% by mass with respect to the total solid content of the coating liquid A. 75-85 mass% is more preferable.

<Water-soluble binder>
The coating liquid A in the present invention contains at least one water-soluble binder. The water-soluble binder in the coating liquid A may be the same or different.
The water-soluble binder may be contained in another coating solution other than the coating solution A as necessary.
However, when the water-soluble binder is contained in the coating liquid B, the content of the water-soluble binder with respect to the pseudo boehmite alumina hydrate in the coating liquid B needs to be less than 3% by mass. When the content is 3% by mass or more, coating defects are deteriorated. From the viewpoint of coating defects, the coating solution B preferably does not contain a water-soluble binder.
Moreover, it is preferable to add the water-soluble binder which does not contain a hydroxyl group to the coating liquid C containing a crosslinking agent as needed, in order to suppress gelatinization with a crosslinking agent.

Examples of the water-soluble binder include, for example, a polyvinyl alcohol-based resin (polyvinyl alcohol (PVA), acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, and silanol-modified resin that has a hydroxyl group as a hydrophilic structural unit. Polyvinyl alcohol, polyvinyl acetal, etc.], cellulosic resins [methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc.] , Chitins, chitosans, starch, resins having an ether bond [polyethylene oxide (PEO , Polypropylene oxide (PPO), polyethylene glycol (PEG), poly ether (PVE)], and resins having carbamoyl groups [polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), polyacrylic acid hydrazide, etc.] and the like.
Moreover, the polyacrylic acid salt which has a carboxyl group as a dissociable group, maleic acid resin, alginate, gelatins, etc. can be mentioned.

  Among the above, the water-soluble binder used in the present invention is at least one selected from polyvinyl alcohol resins, cellulose resins, resins having an ether bond, resins having a carbamoyl group, resins having a carboxyl group, and gelatins. In particular, polyvinyl alcohol (PVA) resin is preferable.

  As the polyvinyl alcohol (PVA) resin, completely or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol can be used. Particularly preferred is a portion having a degree of saponification of 80% or more or a completely saponified product.

  The cation-modified polyvinyl alcohol is, for example, polyvinyl alcohol having primary to tertiary amino groups or quaternary ammonium groups in the main chain or side chain of polyvinyl alcohol as described in JP-A-61-110483. .

From the viewpoint of the strength and ink absorbability of the ink receiving layer, it is preferable to use polyvinyl alcohol having a polymerization degree of 3000 or more as the polyvinyl alcohol-based resin.
The upper limit of the preferable degree of polymerization is about 6000. In the present invention, the degree of polymerization represents an average degree of polymerization. When polyvinyl alcohol having a different average degree of polymerization is used in one layer, it means the average of the respective degrees of polymerization.
In consideration of application suitability and the like, polyvinyl alcohol having a polymerization degree of 3500 or more may be used for the coating solution B.

Further, from the viewpoint of improving ink absorbability and suppressing cracking, the total amount of the water-soluble binder in the ink receiving layer is preferably ² to 8 g / m ² , more preferably ³ to 6 g / m ² .
Further, from the viewpoint of improving ink absorbability and suppressing cracking, the content of the water-soluble binder in the coating liquid A is preferably 10 to 30% by mass with respect to the total solid content of the coating liquid A, and 15 to 25 masses. % Is more preferable.

<Crosslinking agent>
The coating liquid C in the present invention contains at least one crosslinking agent that crosslinks the water-soluble binder. By containing a crosslinking agent, the water-soluble binder can be crosslinked and hardened. Accordingly, the film strength, film formability, and water resistance of the ink receiving layer formed using pseudo boehmite-like alumina hydrate can be improved.
The crosslinking agent may be contained in another coating solution other than the coating solution C as necessary.
However, when the coating agent B is included in the coating solution B, the content of the crosslinking agent with respect to the pseudo boehmite alumina hydrate in the coating solution B needs to be less than 3% by mass. When the content is 3% by mass or more, coating defects are deteriorated. From the viewpoint of coating defects, the coating liquid B preferably does not contain a crosslinking agent.
Similarly, the content of the crosslinking agent in the coating liquid A is also preferably less than 3% by mass with respect to the vapor phase silica in the coating liquid A, and 0% by mass (that is, the coating liquid A contains a crosslinking agent). Is not preferred.

  The crosslinking agent can be used as an aqueous solution in which one or more of them are dissolved in an aqueous solvent. As the aqueous solvent, water such as pure or ion-exchanged water, or a mixed solvent of water and an organic solvent soluble in the water can be used, and details will be described later.

What is necessary is just to select a suitable crosslinking agent suitably in relation to the water-soluble binder contained in an ink receiving layer. Especially, when PVA is contained, boric acid and / or its salt are preferable at the point that a crosslinking reaction is quick. As boric acid, for example, orthoboric acid, metaboric acid, hypoboric acid and the like can be used. As the boric acid salt, these soluble salts (sodium salt, potassium salt, ammonium salt, etc.) are preferable. ₂ B ₄ O ₇ · 10H ₂ O, NaBO ₂ · 4H ₂ 0, K ₂ B ₄ O ₇ · 5H ₂ O, NH ₄ HB ₄ O ₇ · 3H ₂ O, NH ₄ BO _{2 and the} like. However, the present invention is not limited to these.

When gelatin is used in combination with PVA as a water-soluble binder, the following compounds other than boric acid and its salts can also be used as a crosslinking agent.
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; 1,6- Isocyanate compounds such as hexamethylene diisocyanate; Aziridine compounds described in US Pat. Nos. 3,017,280 and 2998611; Carboximide compounds described in US Pat. No. 3,100,704; Epoxys such as glycerol triglycidyl ether Compounds; ethyleneimino compounds such as 1,6-hexamethylene-N, N′-bisethyleneurea; halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; dioxane such as 2,3-dihydroxydioxane Compounds: titanium lactate, aluminum sulfate, chromium alum, potash alum, metal-containing compounds such as zirconyl acetate and chromium acetate, polyamine compounds such as tetraethylenepentamine, hydrazide compounds such as adipic acid dihydrazide, oxazo A low molecule or polymer containing two or more phosphorus groups.

Crosslinking agents may be used alone or in combination of two or more.
The total content of the crosslinking agent in the ink receiving layer is preferably 5 to 40 parts by mass, and more preferably 15 to 35 parts by mass with respect to 100 parts by mass of the total amount of the water-soluble binder. When the content of the crosslinking agent is within the above range, it is effective for preventing cracks and the like.
In the case of using boric acid and / or salts thereof, the total amount of boric acid and / or salt thereof _is preferably 5 to 40 mass% with respect to PVA in H 3 BO ₃ in terms, more preferably 15 to 35 wt% It is. By making the total amount within the above range, it is possible to improve film formability and water resistance while suppressing an increase in viscosity of the coating solution to be prepared.

Further, from the viewpoint of ink absorption and improving the cracking inhibition, as the total amount of the ink receiving layer of the cross-linking agent, preferably ^{0.2~3.0g / m 2, 0.4~1.5g / m} 2 is More preferred.
Further, from the viewpoint of further suppressing coating defects, the content of the crosslinking agent in the ink receiving layer is preferably 2 to 8% by mass, more preferably 3 to 6% by mass with respect to pseudoboehmite-like alumina hydrate. preferable.

<Other ingredients>
The ink receiving layer (that is, at least one of the coating liquid A, the coating liquid B, the coating liquid C, and other coating liquids) in the present invention may contain the following other components as necessary. .

(Cationic compound)
The ink receiving layer of the present invention preferably contains a cationic compound for the purpose of improving water resistance. Examples of the cationic compound include a cationic polymer and a water-soluble metal compound. When the cationic polymer is used in combination with the vapor phase silica, the transparency tends to decrease, and the water-soluble metal compound improves the transparency. This is presumed to suppress fine cracks generated in the ink receiving layer.

  Examples of the cationic compound used in the present invention include a cationic polymer and a water-soluble metal compound. Examples of the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, JP-A-59-20696, 59-33176, 59-33177, 59-1555088, 60-11389, 60- 49990, 60-83882, 60-109894, 62-198493, 63-49478, 63-115780, 63-280681, JP-A-1-40371, 6-234268 No. 7, 7-125411, 10-193976, etc., a polymer having a primary to tertiary amino group or a quaternary ammonium base is preferably used. The molecular weight of these cationic polymers is preferably about 5,000 to 100,000.

  The amount of these cationic polymers used is 1 to 10% by mass, preferably 2 to 7% by mass, based on the inorganic fine particles.

  Examples of the water-soluble metal compound used in the present invention include water-soluble polyvalent metal salts. Examples include water-soluble salts of metals selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten, and molybdenum. Specifically, for example, calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, chloride Cupric, ammonium copper (II) chloride dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, sulfuric acid Nickel ammonium hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, chloride Ferrous, ferric chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, bromide Lead, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zirconium acetate, zirconium chloride, chlorinated zirconium oxide octahydrate, hydroxy zirconium chloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, citrate Examples include magnesium nitrate nonahydrate, sodium phosphotungstate, sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstophosphoric acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, and the like. . Among them, a zirconium-based compound having a high effect of improving transparency and water resistance is preferable.

Examples of the cationic compound include a basic polyaluminum hydroxide compound that is an inorganic aluminum-containing cationic polymer. The basic polyaluminum hydroxide compound has a main component represented by the following general formula 1, 2 or 3, for example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ⁴⁺ , [Al ₁₃ (OH) ₃₄ ] ⁵⁺ , [Al ₂₁ (OH) ₆₀ ] ³⁺ , and the like are water-soluble polyaluminum hydroxides that stably contain basic and high-molecular polynuclear condensed ions.

_{[Al 2 (OH) n Cl} 6-n] m ··· Formula 1
[Al (OH) ₃ ] _n AlCl ₃ Formula 2
Al _n (OH) _m Cl _(3n-m) , 0 <m <3n Formula 3

  These are water treatment agents from Taki Chemical Co., Ltd. under the name of polyaluminum chloride (PAC), from Asada Chemical Co., Ltd. under the name of polyaluminum hydroxide (Paho), and from Riken Green Co., Ltd. It is marketed under the name of Purachem WT and from other manufacturers for the same purpose, and various grades can be easily obtained. In the present invention, these commercially available products can be used as they are, but there are also products having an inappropriately low pH, and in that case, the pH can be appropriately adjusted and used.

In the present invention, the content of the ink receiving layer of the water-soluble metal ^{compound, 0.1g / m 2 ~10g / m} 2, and preferably from ^{0.2g / m 2 ~5g / m 2} .

  Two or more of the above cationic compounds can be used in combination. For example, a cationic polymer and a water-soluble metal compound may be used in combination.

  The ink receiving layer in the present invention preferably contains various oil droplets in order to improve the brittleness of the film. Such oil droplets have a hydrophobicity of 0.01% by mass or less in water at room temperature. High-boiling organic solvents (for example, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil) and polymer particles (for example, styrene, butyl acrylate, divinylbenzene, butyl methacrylate, hydroxyethyl methacrylate, etc.) One or more kinds of polymerized particles) can be contained. Such oil droplets can be preferably used in the range of 10 to 50% by mass relative to the hydrophilic binder.

(Hardener)
In the present invention, a hardening agent other than the above crosslinking agent can be added to the ink receiving layer for the purpose of improving water resistance and dot reproducibility. Specific examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1 , 3,5 triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, N-methylol compounds as described in Japanese Patent No. 2,732,316, isocyanates as described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280 and 2,983,611 described Aziridines such as carbodiimide compounds as described in US Pat. No. 3,100,704, Such epoxy compounds described No. 3,091,537, such as halogen carboxy aldehydes mucochloric acid, such as dioxane derivatives of dihydroxy dioxane, chromium alum, there is a zirconium sulfate and the like. Preferably, by using an organic titanium compound in combination with boric acid or borate, the thixotropic coefficient can be increased without greatly increasing the viscosity.

  In the present invention, in addition to the surfactant and the hardener, the ink receiving layer further includes a coloring dye, a coloring pigment, an ink dye fixing agent, an ultraviolet absorber, an antioxidant, a pigment dispersant, and an antifoaming agent. , Various known additives such as leveling agents, preservatives, optical brighteners, viscosity stabilizers, and pH adjusters may be added.

<Support>
The support in the present invention is not particularly limited as long as it can form an ink-receiving layer. For example, a base paper or a water-resistant support may be used.
Although there is no limitation in particular as thickness of a support body, 50-250 micrometers is preferable.

(Base paper)
Examples of the base paper include virgin pulp such as chemical pulp such as LBKP, NBKP, LBSP, NBSP, LUKP, NUKP, LUSP, and NUSP, and mechanical pulp such as GP and TMP, recycled paper from newspapers, magazines, and office paper Paper made using pulp can be used.

The base paper has at least one white pigment having an average particle size of 0.3 to 10 μm as a filler, for example, calcium carbonate, magnesium carbonate, talc, kaolin, silica, alumina, titanium dioxide, barium sulfate, etc. Is used in an amount of 2 to 30% by mass, preferably 4 to 30% by mass. If the average particle size of the white pigment is 0.3 μm or more, the yield can be further improved, and if the average particle size of the white pigment is 10 μm or less, the texture of the paper can be further improved.
In particular, a white pigment having a whiteness degree defined by JIS-M8016 of 88% or more is preferably used. If the white pigment content is 2% by mass or more, a white base paper can be obtained, and if the white pigment content is 30% by mass or less, the strength of the base paper can be further improved. Dirt can be further suppressed.
Various sizing agents, paper strength enhancing agents, antistatic agents, fluorescent whitening agents, dyes and the like generally used in papermaking are blended with the base paper.

  Further, a surface sizing agent, a surface paper strengthening agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchor agent, and the like may be applied to the base paper.

  The thickness of the base paper is preferably 70 to 200 μm. The thickness is adjusted by applying pressure on the paper during paper making or after paper making and compressing it.

When using base paper as a support in the present invention, it is preferable to further include a step of calendering the surface of the formed ink receiving layer from the viewpoint of glossiness and the like. The calendar process can be performed by, for example, a calendar device having a mirror roll (mirror drum).
As the calendering conditions, the temperature of the re-wetting liquid to be brought into contact with the uppermost layer between the nip between the heated mirror drum surface and the pressure roll is 92 ° C. or higher, preferably 95 ° C. or higher, and the wetting time is 25 mm seconds. In the following, it is preferable that the time is preferably 20 mm seconds or less, and the temperature of the mirror drum surface that presses the uppermost layer in a wet state is 95 ° C or higher, preferably 97 ° C or higher.

(Water resistant support)
As the water-resistant support, polyethylene, polypropylene, polyvinyl chloride, diacetate resin, triacetate resin, cellophane, acrylic resin, polyethylene terephthalate, polyethylene naphthalate film, resin-coated paper, or the like is used.

The resin-coated paper refers to one in which at least one side (preferably both sides) of the above-mentioned base paper is coated with a resin.
As the resin, low density polyethylene, density 0.94~0.96g / cm ³ density polyethylene having a density of 0.91~0.93g / cm ^3, medium density polyethylene of medium density, polypropylene, polybutene, Polyolefin, homopolymer of olefin such as polypentene or copolymer composed of two or more olefins such as ethylene-propylene copolymer and a mixture thereof, polyolefin resin, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, polystyrene, etc. Those having various densities and melt viscosity indices (melt index) can be used alone or in combination. In particular, a polyolefin resin is preferably used from the viewpoint of handleability, and it is particularly preferable to contain 50% by mass or more of low density polyethylene having a density of 0.91 to 0.93 g / cm ³ in the total resin solid content of the resin coating layer.

  Further, in the resin coating layer on the side where the ink receiving layer is provided on at least the resin-coated paper, white particles such as titanium dioxide, barium sulfate, zinc oxide, calcium carbonate, magnesium carbonate having an average particle diameter of 0.1 to 1 μm. At least one pigment can be contained in an amount of 5 to 20% by mass, preferably 7 to 15% by mass, based on the solid content of the total resin. A white pigment having an average particle size of less than 0.1 μm has a hiding effect, and if it is greater than 1 μm, the surface properties of the resin layer deteriorate. In particular, a white pigment having a whiteness degree defined by JIS-M8016 of 88% or more is preferably used. By setting the white pigment to 5% by mass or more based on the solid content of the resin, sufficient opacity of the resin-coated paper can be obtained even when the thickness of the base paper is thin. Moreover, by setting it as 20 mass% or less, the nonuniformity by the generation | occurrence | production of a crack etc. on the surface of a resin layer is suppressed, and intensity | strength can be maintained. Other additives include fatty acid amides such as stearic acid amide and arachidic acid amide, fatty acid metal salts such as zinc stearate, calcium stearate, aluminum stearate and magnesium stearate, antioxidants such as Irganox 1010 and Irganox 1076, Various additives such as blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue, and phthalocyanine blue, magenta pigments and dyes such as cobalt violet, fast violet, and manganese purple, fluorescent whitening agents, and UV absorbers are appropriately used. Add in combination.

  The main production method of the resin-coated paper is produced by a so-called extrusion coating method in which a thermoplastic resin is cast on a traveling base paper in a heated and melted state, and the base paper is coated with the resin. Further, before the resin is coated on the base paper, the base paper is preferably subjected to an activation treatment such as corona discharge treatment or flame treatment. The resin coating layer on the back surface is usually a matte surface, and an active treatment such as a corona discharge treatment or a flame treatment can be applied to the front surface or both the front and back surfaces as necessary.

  The front side resin layer on which the ink receiving layer of the resin-coated paper is formed is obtained by mainly heating and melting a thermoplastic resin on one side of the base paper with an extruder, extruding it into a film between the base paper and a cooling roll, pressing and cooling. Manufactured. At this time, the cooling roll is used to form the surface shape of the resin coating layer, and the surface of the resin layer is processed into a mirror surface, a fine rough surface, or a patterned silk or mat shape depending on the shape of the surface of the cooling roll. can do.

  The back side resin layer opposite to the front side resin layer of the resin-coated paper can also be produced by heating and melting the resin with an extruder, extruding it into a film between the base paper and a cooling roll, pressing and cooling. At this time, preferably, from the viewpoint of transportability in the printer, the cooling roll is preferably a finely roughened surface or patterned depending on the shape of the cooling roll surface so that Ra specified in JIS-B-0601 is 0.8 to 5 μm. For example, it is preferable to mold the material into a silky shape or a mat shape.

  The method of providing the resin coating layer on the base paper includes the method of irradiating the electron beam after applying the electron beam curable resin, in addition to extruding the heated molten resin, and drying after applying the coating solution of the polyolefin resin emulsion. And a method of performing a surface smoothing treatment. In any case, a resin-coated paper applicable to the present invention can be obtained by performing molding with a hot roll having irregularities.

An undercoat layer may be provided on the front side surface of the resin-coated paper in order to improve adhesion. The undercoat layer is applied and dried in advance on the surface of the resin layer of the support before the ink receiving layer is applied. The undercoat layer is a layer mainly comprising a water-soluble polymer capable of forming a film, a polymer latex or the like, and preferably a water-soluble polymer such as gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, or water-soluble cellulose is used. Preferably it is formed using gelatin. 10-500 mg / m < ² > is preferable and, as for the adhesion amount of a water-soluble polymer, 20-300 mg / m < ² > is more preferable. The undercoat layer preferably further contains a surfactant or a hardener. Moreover, it is preferable to perform a corona discharge treatment before forming the undercoat layer (by coating or the like) on the resin-coated paper.

  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. Further, in this example, an example of producing an ink jet recording sheet as an example of the ink jet recording medium is mainly shown.

[Example 1]
<Preparation of pseudo boehmite-like alumina hydrate dispersion>
While stirring 2042 g of ion-exchanged water with a dissolver, 708 g of Cataloid AP-5 (Pseudo Boehmite Alumina Hydrate; average primary particle diameter of 8 nm, manufactured by Catalytic Chemical Industry Co., Ltd.) was added thereto, and a white coarse dispersion of alumina Got. The number of revolutions of the dissolver at this time was 3000 rpm, and the rotation time was 10 minutes.

  Subsequently, this coarse alumina dispersion was finely dispersed with a high-pressure disperser (Ultimizer HJP25005, manufactured by Sugino Machine Co., Ltd.), and a white transparent alumina dispersion having a solid content concentration of 25% (pseudo boehmite-like alumina hydrate). Product dispersion). The pressure at this time was 100 MPa, and the discharge rate was 600 g / min.

  About the obtained pseudo boehmite-like alumina hydrate dispersion, the particle size of dispersed particles was adjusted with LB-500 (manufactured by Horiba, Ltd.) with the liquid temperature adjusted to 30 ° C. and diluted with ion-exchanged water. Was measured. As a result of the measurement, the particle diameter was 0.06 μm.

<Preparation of gas phase method silica dispersion>
While stirring 3365 g of ion-exchanged water with a dissolver, 35 g of Charol DC902P (diallyldimethylammonium chloride manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added, and Aerosil 300 (gas phase method silica manufactured by Nippon Aerosil Co., Ltd.); average primary particle size 7 g) was added to obtain a gas phase silica crude dispersion. At this time, the rotational speed of the dissolver was 3000 rpm, and the rotational time was 10 minutes. This crude vapor phase silica dispersion was finely dispersed with a high-pressure disperser (Ultimizer HJP25005 manufactured by Sugino Machine Co., Ltd.) to obtain a white transparent vapor phase silica dispersion having a solid content concentration of 15% by mass. The pressure at this time was 100 MPa, and the discharge rate was 600 g / min. The particle diameter of the dispersed particles in the transparent silica dispersion was measured by the same method as that for the dispersed particles in the pseudo boehmite-like alumina hydrate dispersion, and found to be 0.1040 μm.

<Preparation of coating liquid C (top layer)>
200 g of 7.5% boric acid aqueous solution, 150 g of 8% concentration Alcox R1000 (polyethylene oxide manufactured by Meisei Chemical Co., Ltd.) and 4 g of 10% surfactant aqueous solution (Swanol AM2150 manufactured by Nikko Chemicals Co., Ltd.) are mixed and applied. Liquid C (the uppermost layer) was obtained. Here, the “uppermost layer” refers to a layer farthest from the support in the simultaneous multilayer coating described later.

<Preparation of coating liquid B (intermediate layer)>
937.5 g of the pseudo boehmite-like alumina hydrate dispersion obtained above and 12.3 g of a 10% surfactant aqueous solution (Swanol AM2150 manufactured by Nikko Chemicals Co., Ltd.) were mixed to obtain a coating solution B (intermediate layer). ) Here, the “intermediate layer” refers to a layer located between the “uppermost layer” and the “lowermost layer” described later in the simultaneous multilayer coating described later.

<Preparation of coating liquid A (lowermost layer)>
892.2 g of the vapor phase silica dispersion obtained above, 467.4 g of 7% aqueous solution of polyvinyl alcohol (PVA245 manufactured by Kuraray Co., Ltd.) having a saponification degree of 88% and a polymerization degree of 4500, and a 10% surfactant aqueous solution ( 16.2 g of Nikko Chemicals Co., Ltd. Swanol AM2150), 84.2 g of ion-exchanged water, and 160 g of 59% AP-7 (Nihon Alcohol Industrial Ethanol) were kept at 30 ° C. before mixing. The liquids that had been kept warm were mixed well while being kept at 30 ° C. to obtain a coating liquid A (lowermost layer). Here, the “lowermost layer” refers to a layer closest to the support in the simultaneous multilayer coating described later.

<Production of support>
A 1: 1 mixture of hardwood bleached kraft pulp (LBKP) and softwood bleached sulfite pulp (NBSP) was beaten to 300 ml with Canadian Standard Freeness to prepare a pulp slurry. In the obtained pulp slurry, the alkyl ketene dimer as a sizing agent is 0.5 mass% with respect to the pulp, the polyacrylamide as the strength agent is 1.0 mass% with respect to the pulp, and the cationized starch with 2.0 mass% with respect to the pulp. Polyamide epichlorohydrin resin was added at 0.5% by mass to the pulp, respectively, and diluted with water to give a 1% slurry.
This 1% slurry was made into a paper having a basis weight of 170 g / m ² using a long paper machine, dried and conditioned to obtain a base paper.

Next, a polyethylene resin composition in which 10% by mass of anatase-type titanium was uniformly dispersed with respect to 100% by mass of low-density polyethylene having a density of 0.918 g / cm ³ was melted at 320 ° C. The melted polyethylene resin composition was extrusion-coated on one side of the base paper obtained above so as to have a thickness of 35 μm at 200 m / min, and extrusion-coated using a cooling roll having a finely roughened surface ( Hereinafter, this surface is sometimes referred to as the “front side” of the polyolefin resin-coated paper).

It was then melt blended resin composition with low density polyethylene resin 30 parts by weight of a density 0.962 g / cm high-density polyethylene resin 70 parts by weight of ³ and a density 0.918 g / cm ³ at 320 ° C.. The melted blend resin composition was extrusion coated on the other side of the base paper to a thickness of 30 μm, and extrusion coated using a roughened cooling roll (hereinafter, this side was coated with polyolefin resin coated paper). Sometimes called “back side”).

Thus, a polyolefin resin-coated paper was obtained.
Next, the front surface of the obtained polyolefin resin-coated paper was subjected to high-frequency corona discharge treatment, and then the undercoat layer having the following composition was applied and dried so that the lime-treated gelatin was 50 mg / m ² , thereby supporting the water resistance. A body (support) was obtained.

~ Composition of undercoat layer ~
・ Lime-processed gelatin: 100 parts ・ Sulfosuccinic acid-2-ethylhexyl ester salt: 2 parts ・ Chrome alum: 10 parts

<Formation of ink receiving layer>
First, the coating liquid A, the coating liquid B, and the coating liquid C obtained above were each kept at 45 ° C.
Next, the coating liquid A, the coating liquid B, and the coating liquid C were simultaneously coated on the undercoat layer of the support by a slide bead coating apparatus so as to be in this order when viewed from the support side (simultaneous multilayer coating). ).
Here, the simultaneous multi-layer coating is 6 g / m ² of boric acid in the coating solution C (uppermost layer), 20 g / m ^{2 of} pseudoboehmite-like alumina hydrate in the coating solution B (intermediate layer), and the coating solution A. The coating amount was 9 g / m ² in the vapor phase silica in the (lowermost layer).

Next, the coating film obtained by the above coating is cooled for 30 seconds so that the film surface temperature becomes 12 ° C., and further, the conditions of 45 ° C. and 10% RH until the total solid content concentration becomes 90% by mass. And then dried under conditions of a temperature of 35 ° C. and 10% RH.
Next, the dried coating film was set and dried for 2 minutes so that the film surface temperature was 20 ° C., and then dried at 80 ° C. for 10 minutes.
As described above, an ink receiving layer was formed on the undercoat layer to obtain an ink jet recording sheet.
The total thickness of the formed ink receiving layer was 45 μm.

<Evaluation>
The following evaluation was performed using the inkjet recording sheet obtained above. The evaluation results are shown in Table 1.
(1) Print density Black solid printing was performed on the ink receiving layer of the inkjet recording sheet using an Seiko Epson inkjet printer PM-A820. The image density of the black (Bk) solid print portion was measured using Gretag Spectrolino SPM-50 under the conditions of a viewing angle of 2 °, a light source D50, and no filter.

(2) Glossiness The glossiness of the ink receiving layer surface of the ink jet recording sheet before printing is measured using a digital variable glossmeter (UGA-5D measuring hole 8 mm), incident angle 60 degrees, light reception. Measurements were made at 60 degrees.

(3) Application defects When 100 m ^{2 of the} inkjet recording sheet was produced, the occurrence of partial defects and application unevenness of 3 mm or more per 100 m ² was visually observed and compared according to the following criteria.
~ Evaluation criteria ~
A: 1 or less partial defects B: 2 to 10 partial defects C: 11 to 100 or more partial defects D: 101 to 1000 or more partial defects
E: There are 1001 to 2000 or more partial defects.

[Example 2]
The cross-linking agent of coating solution C (uppermost layer) is changed to adipic acid dihydrazide, and the water-soluble binder of coating solution A (lowermost layer) is changed to acetoacetyl-modified PVA (Nippon Gosei Chemical Co., Ltd. Goseifamer Z210; degree of acetoacetylation) An ink jet recording sheet was prepared in the same manner as in Example 1 except that the content was changed to 3%, saponification degree 98%, polymerization degree 2350).
The obtained ink jet recording sheet was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3
An inkjet recording sheet was produced in the same manner as in Example 1 except that the preparation of the pseudo boehmite-like alumina hydrate dispersion was changed as follows.
The obtained ink jet recording sheet was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Preparation of pseudo boehmite-like alumina hydrate dispersion>
Ion-exchanged water 1200 g and isopropyl alcohol 900 g were charged into a 3 L reactor and heated to 75 ° C. 408 g of aluminum isopropoxide was added to the heated solution, and hydrolysis was performed at 75 ° C. for 24 hours and at 95 ° C. for 4 hours. Thereafter, 24 g of acetic acid was added, and the mixture was stirred at 95 ° C. for 48 hours, and then concentrated so that the solid concentration was 15%, to obtain a white alumina hydrate dispersion (alumina white transparent dispersion).
When this sol (alumina white transparent dispersion) was dried at room temperature and measured for X-ray diffraction, it showed a pseudoboehmite structure. Further, when the average primary particle diameter was measured with a transmission electron microscope, it was about 30 nm and was an alumina hydrate having a flat pseudoboehmite structure with an aspect ratio of 6. Further, when the BET specific surface area, the average pore radius, the pore volume with a pore radius of 1 nm to 30 nm, and the pore volume with a pore radius of 2 nm to 10 nm were measured by a nitrogen adsorption / desorption method, 136 m ² / g, 5 0.8 nm, 0.54 ml / g, and 0.50 ml / g.

Example 4
An ink jet recording sheet was produced in the same manner as in Example 1 except that the vapor phase silica was changed from Aerosil 300 to Aerosil OX50 (average primary particle size 40 nm).
The obtained ink jet recording sheet was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 5
2 parts of potassium oleate is added to the coating solution B (intermediate layer) with respect to pseudoboehmite-like alumina hydrate, and the method for preparing the support is changed to the following method. An ink jet recording sheet was produced in the same manner as in Example 1 except that it was applied.
The obtained ink jet recording sheet was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Production of support>
A pigment having a ratio of light calcium carbonate, heavy calcium carbonate and talc of 10/10/10 to 100 parts of wood pulp comprising 80 parts of LBKP (freeness 400 mlcsf) and 20 parts NBKP (freeness 400 mlcsf) 25 parts, 0.10 parts of commercially available alkyl ketene dimer, 0.03 parts of commercially available cationic (meth) acrylamide, 0.80 parts of commercially available cationized starch, and 0.40 parts of sulfuric acid band to prepare a mixture Was used to obtain a base paper (support) having a basis weight of 90 g / m ² .

<Calendar processing>
An ink receiving layer was formed on the base paper obtained above by the same method as in Example 1.
On the surface of the ink receiving layer thus formed, a rewet cast (calendar treatment) was performed under the following conditions using a device comprising a pressure contact roll having a diameter of 300 mm and a mirror drum having a diameter of 1250 mm and a nozzle disposed on the nip. ) To obtain an ink jet recording sheet (ink jet cast coated paper).

-Rewet cast conditions-
Re-wetting liquid used: Hot water Re-wetting liquid temperature: 95 ° C
Mirror surface temperature: 95 ° C
Press nip pressure: 150 kg / cm ²
Wetting time: 20 milliseconds

[Comparative Example 1]
An ink jet recording sheet was prepared in the same manner as in Example 1 except that boric acid was added to the coating liquid B (intermediate layer) without using the coating liquid C (uppermost layer).
The obtained ink jet recording sheet was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 2]
An inkjet recording sheet was prepared in the same manner as in Example 1 except that the coating liquid C (uppermost layer) was not used and boric acid was added to the coating liquid A (lowermost layer).
The obtained ink jet recording sheet was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 3]
An inkjet recording sheet was prepared in the same manner as in Example 1 except that 7% aqueous solution of polyvinyl alcohol (PVA245 manufactured by Kuraray Co., Ltd.) having a saponification degree of 88% and a polymerization degree of 4500 was added to the coating liquid B (intermediate layer). did.
The obtained ink jet recording sheet was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 4]
An ink jet recording sheet was prepared in the same manner as in Example 1 except that 7% aqueous solution of polyvinyl alcohol (PVA245 manufactured by Kuraray Co., Ltd.) having a saponification degree of 88% and a polymerization degree of 4500 was not added to the coating liquid A (lowermost layer). Produced.
The obtained ink jet recording sheet was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  As shown in Table 1, in the inkjet recording sheets of Examples 1 to 5, a high printing density was exhibited and coating defects were suppressed. On the other hand, Comparative Example 1 in which the coating liquid B was allowed to contain a crosslinking agent without using the coating liquid C, Comparative Example 2 in which the coating liquid A was made to contain a crosslinking agent without using the coating liquid C, and a water-soluble binder was added to the coating liquid B. In Comparative Example 3 containing the coating defects, the coating defects deteriorated. Further, in Comparative Example 3 in which the coating liquid B contains a water-soluble binder, the printing density was lowered. In Comparative Example 4 in which the coating liquid A did not contain a water-soluble binder, the coating film (ink receiving layer) could not be formed.

Claims (4)

On the support, at least,
(A) a coating solution A containing vapor phase silica and a water-soluble binder;
(B) a pseudo boehmite-like alumina hydrate, wherein the content of the water-soluble binder with respect to the pseudo-boehmite-like alumina hydrate and the content of the crosslinking agent with respect to the pseudo-boehmite-like alumina hydrate are both less than 3% by mass A coating liquid B,
(C) a coating solution C containing a crosslinking agent;
A method for producing an ink jet recording medium, comprising a step of forming an ink receiving layer by coating the substrate from the support side in this order.   2. The method for producing an ink jet recording medium according to claim 1, wherein the vapor phase silica and the pseudo boehmite-like alumina hydrate have an average primary particle diameter of 3 to 20 nm.   3. The method for manufacturing an ink jet recording medium according to claim 1, further comprising a step of calendering the surface of the formed ink receiving layer, wherein the support is a base paper.   The method for producing an ink jet recording medium according to claim 1, wherein the support is a water-resistant support.