JP2010234722A - Inkjet recording material and method for preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording material which is excellent in outward appearance and free from cracking and has a high color-developing density and a photographic property. <P>SOLUTION: The inkjet recording material is prepared by a process in which a water dispersion constituted mainly of inorganic fine particles and polyvinyl alcohol and a water dispersion of one or more crosslinking agents selected from compounds containing boron, zirconium and titanium having a function of crosslinking the polyvinyl alcohol are atomized in the range of an average particle diameter of 10-300 μm using a two-fluid nozzle and sprayed, mixed and applied on at least one surface of a substrate. The inkjet recording material is prepared, in addition, by applying the water dispersion constituted mainly of the inorganic fine particles and the polyvinyl alcohol on the surface of an image recording material thus obtained, using a curtain coating apparatus. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ink jet recording material. Specifically, the present invention relates to a photographic grade ink jet recording material excellent in printability.

  Inkjet recording is free of noise and can be printed at high speed, and is used in terminal printers and the like, and has been rapidly spreading in recent years. Further, by using a plurality of ink two-fluid nozzles, it is easy to perform multi-color recording, and multi-color ink jet recording is performed by various ink jet recording methods. In particular, the use of an ink jet printer capable of forming a complex image quickly and accurately as a hard copy production apparatus for image information such as characters, various figures and photographs created by a computer has attracted attention. In recent years, with the rapid spread of digital cameras, digital photographic images have become familiar, and inkjet printers equipped with a photographic-only mode and ink for outputting these images with an inexpensive inkjet printer are also rapidly spreading.

  In ink jet recording, it is important that ink is quickly absorbed and fixed to the recording material in a state where the ink reaches the recording material. When ink reaches the surface without being absorbed, and another ink arrives, the ink spreads and color reproducibility is impaired, and the resolution of the image is greatly affected. Further, while an ink absorption speed is required, it is important to secure an ink absorption capacity. That is, in inkjet recording, the number of inks increases due to the increase in color, and the total amount of ink per unit area is high in order to obtain high color reproducibility. When the ink absorption capacity of the recording material is insufficient, the ink overflows on the surface of the recording material.

  In order to solve this problem, an ink jet recording material in which a porous ink receiving layer using extremely fine inorganic fine particles is coated on a support is preferably used as the recording material. Such an ink jet recording material exhibits excellent characteristics in ink absorption capacity, color density, and gloss. A method using vapor-phase silica as inorganic fine particles capable of forming an ultrafine and ink-receiving layer having an ink absorption capability (for example, Patent Document 1), a method using finely pulverized wet method silica (for example, Patent Document 2 or 3) And a method using an alumina hydrate such as boehmite (for example, Patent Document 4). All of these are ultrafine particles having an average primary particle size of several tens of nm or less, and ink is absorbed and held in abundant voids, so that a high ink absorption capacity is obtained. Also, the average particle size of the primary particles is shorter than the wavelength of visible light, the optical transparency of the ink receiving layer is high, and the ink that has penetrated the ink receiving layer is not shielded, so a high print density and a sharp image can be obtained. Has characteristics.

  On the other hand, in the case of using inorganic fine particles to obtain a high ink absorption capacity, the coating layer strength is low, the print surface is likely to be damaged, and the ink receiving layer is likely to fall off due to bending. In order to solve this problem, a device has been devised such as adding an additive that contributes to crosslinking of the binder to the ink receiving layer. Specifically, a method of adding polyaluminum chloride (for example, Patent Document 5), a method of adding a zirconium compound (for example, Patent Document 6), a method of containing an acetoacetyl group-modified polyvinyl alcohol and its crosslinking agent (for example, Patent Document 7 or 8). However, in such a method of adding a crosslinking agent, in the state of the coating liquid before forming the ink receiving layer, the crosslinking agent acts on the binder and the liquid tends to increase in viscosity or gel, In some cases, defects such as cracks in the coating layer may occur, and a serious problem may occur in productivity, such as the necessity to significantly reduce the coating speed.

  As a method for solving such a gelation problem of the coating solution, the polyvinyl alcohol as a binder and the cross-linking agent are separately applied to the upper and lower layers, that is, the cross-linking agent acts on the polyvinyl alcohol through the applied interface to advance the cross-linking. There is a method (for example, Patent Document 9). In such a method, there is no problem of gelation of the coating solution, but there is a problem that sufficient crosslinking effect cannot be obtained because crosslinking is most likely to proceed at the coating layer interface and resistance of movement of the crosslinking agent is generated. .

Japanese Patent Laid-Open No. 10-81064 JP-A-9-286165 JP-A-10-181190 Japanese Patent Laid-Open No. 6-199034 Japanese Patent Publication No. 8-118787 Japanese Patent Publication No. 6-32046 JP 63-176173 A Japanese Patent Laid-Open No. 10-157283 JP 2007-38651 A

  An object of the present invention is to provide a photo-like ink jet recording material that is excellent in appearance, has no cracks, and has a high color density.

  In the present invention, at least one surface on the support is selected from one or more compounds containing inorganic fine particles and an aqueous dispersion mainly composed of polyvinyl alcohol and a compound containing boron, zirconium, and titanium having a function of crosslinking polyvinyl alcohol. This is achieved by an ink jet recording material characterized in that the aqueous dispersion of the cross-linking agent is atomized into a spray state, mixed and applied to a support. Furthermore, the ink jet recording material is more preferably achieved by an ink jet recording material in which an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol is curtain-coated on the coated surface of the obtained ink jet recording material.

  Further, the present invention provides one or more compounds containing boron, zirconium, and titanium having a function of cross-linking polyvinyl alcohol and an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol on at least one surface on the support. This is achieved by a method for producing an ink jet recording material, characterized in that an aqueous dispersion of a selected crosslinking agent is atomized using a two-fluid nozzle to form a spray state, mixed, and coated on a support. Furthermore, it is more preferably achieved by a method for manufacturing an inkjet recording material, which includes a step of applying an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol on a coating surface of the inkjet recording material using a curtain coating apparatus. The

  By practicing the present invention, a photo-like ink jet recording material having an excellent appearance, no cracking, and a high color density can be obtained.

Schematic cross-section of internal mixing type two-fluid nozzle Schematic cross-section of externally mixed two-fluid nozzle

  In the present invention, the polyvinyl alcohol and its cross-linking agent are each dispersed in water after being sprayed by a two-fluid nozzle, so that the cross-linking of the polyvinyl alcohol with the cross-linking agent can proceed efficiently and promptly. That is, the sprayed aqueous dispersion is in the form of fine particles, has a large specific surface area, and has a very high collision probability between the crosslinking agent and polyvinyl alcohol. In addition, since the aqueous dispersion is a fine particle droplet, the diffusion rate of material diffusion inside the droplet is also higher than that of the method in which cross-linking proceeds through the interface between the upper and lower layers. The fine particles of the sprayed aqueous dispersion referred to here are preferably 10 to 300 μm in size. When the particle size of the aqueous dispersion fine particles is less than 10 μm, there is a problem that moisture evaporates quickly, the particles are not sufficiently mixed with each other, and the crosslinking is difficult to proceed, and the gloss of the ink receiving layer is lowered. When the particle size of the aqueous dispersion fine particles is larger than 300 μm, the crosslinking reaction proceeds only at the particle interface, so that irregularities and cracks of the coating layer occur in the ink receiving layer, the appearance is impaired, and ink absorption unevenness occurs. The particle diameter of the aqueous dispersion fine particles was measured with a laser diffraction particle size measuring device (sysmex Mastersizer 2000).

  The two-fluid nozzle in the present invention is a spray nozzle that atomizes an aqueous dispersion with a high-speed air flow and sprays it from the nozzle. The shape of the two-fluid nozzle is provided with an orifice tube outlet that introduces a water dispersion liquid into the air having a velocity component in the nozzle outlet direction shown in FIG. The liquid is mixed inside the chamber to atomize the aqueous dispersion, and the nozzle outlet is squeezed to further atomize when sprayed into the atmosphere, and the aqueous dispersion shown in FIG. 2 is ejected into the atmosphere. An air mixing nozzle is provided in the direction of the concentric circle of the one-fluid nozzle, and high-speed air is ejected to atomize and spray the aqueous dispersion. The external mixing type is a method suitable for coating operation because the particle size of the aqueous dispersion fine particles is larger than that of the internal mixing type, but the spray amount per hour can be increased. The particle diameter of the sprayed water dispersion fine particles can be controlled by the flow rates and ratios of the gas and liquid before mixing and the diameter of the nozzle before being discharged to atmospheric pressure. In addition, two fluid nozzles of an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol and an aqueous dispersion of a polyvinyl alcohol crosslinking agent are placed facing each other at the opposite position, and both are mixed immediately after spraying. Then, since the speed of the water-dispersed particles is high and the kinetic energy is high, the fine particles of the water-dispersed liquid can be further subdivided by the collision of the particles, the particle diameter can be reduced, and the mixing efficiency can be increased. Further, in the flow direction of the support, a two-fluid nozzle for spraying both an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol and an aqueous dispersion of a polyvinyl alcohol crosslinking agent is brought close to the support and mixed in a sprayed state. There is also a method of spraying and coating in parallel toward the support.

  In the present invention, it is more preferable to provide an ink receiving layer (hereinafter referred to as an upper layer) by curtain coating on the ink receiving layer formed by coating with a two-fluid nozzle. By providing an upper layer on the ink receiving layer formed by the two-fluid nozzle without passing through the drying step or by using a non-contact curtain coating device after drying, an ink jet recording material with higher gloss can be obtained. . Further, when polyvinyl alcohol is used for the upper layer, cross-linking occurs at the interface between the ink receiving layer and the upper layer by the cross-linking agent, and high coating layer strength can be obtained.

  The cross-linking agent contained in the aqueous dispersion of the cross-linking agent in the present invention (hereinafter referred to as cross-linking agent liquid) acts on polyvinyl alcohol to form a cross-linked structure, and boric acid, borax, and zirconium-containing compounds are used as boron-containing compounds. Examples of zirconium carbonate, zirconium acetate, zirconium oxychloride, zirconium sulfate, and titanium-containing compounds include titanium lactate and titanium triethanolamate.

  As the inorganic fine particles in the present invention, it is preferable to use silica or alumina hydrate. When such inorganic fine particles are used, ink absorption capacity, image sharpness, and gloss can all be increased. In particular, inorganic fine particles capable of forming a layer having a large absorption capacity, having a suitable refractive index, and obtaining a microporous structure are preferably gas phase method silica and wet method silica as silica, and boehmite, pseudoboehmite, γ alumina or alumina as alumina. These mixed structures are preferable, and boehmite is particularly preferable. In any case, various organic treatments and inorganic treatments can be applied for the purpose of improving dispersibility and modifying optical properties.

  The average particle size of silica used in the ink receiving layer in the present invention is 40 nm or less as an average primary particle size in the case of gas phase method silica, and 1 μm or less as an average secondary particle size in the case of wet method silica. Is preferred. The average primary particle diameter can be determined by directly measuring the particle diameter in high-magnification observation at 100,000 to 300,000 times by SEM. The secondary particle size can be measured by using a laser diffraction / scattering particle size distribution measuring device Partica LA-950 manufactured by HORIBA.

  The wet method silica in the present invention is classified into precipitation method silica, gel method silica, sol method silica and the like according to the production method. Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the silica particles that have grown are agglomerated and settled, and are then commercialized through filtration, water washing, drying, pulverization and classification. The secondary particles of precipitated silica become loosely aggregated particles, and particles that are relatively easy to grind are obtained. Precipitated silica is commercially available, for example, from Tosoh Silica Co., Ltd. as a nip seal and from Tokuyama Co., Ltd. as a Toxeal. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. In this case, the small silica particles dissolve during ripening and reprecipitate so that the primary particles are bonded to each other between the primary particles of the large particles, so that the clear primary particles disappear and a relatively hard agglomeration having an internal void structure Form particles. For example, it is marketed as Mizusukasil from Mizusawa Chemical Industry Co., Ltd. and as a silo jet from Grace Japan Co., Ltd. The sol silica is also referred to as colloidal silica, and is produced by heating and aging silica sol obtained through metathesis of sodium silicate acid or the like through an ion exchange resin layer, and is commercially available from, for example, Nissan Chemical Co., Ltd. as Snowtex. As another method, colloidal silica is produced by an alkoxide hydrolysis method or the like.

  In addition to silica or alumina, an inorganic pigment can be mixed in the aqueous dispersion in the present invention. As the inorganic pigment to be mixed, titanium oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, talc, kaolin, calcined kaolin, activated clay, diatomaceous earth, mica and the like can be used alone or in any mixture. The mixing ratio with respect to silica or alumina is preferably 40% by mass or less.

  In the present invention, it is preferable to use polyvinyl alcohol as the binder. Polyvinyl alcohol is fully or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol. Particularly preferred among the polyvinyl alcohols are those having a saponification degree of 80% or more or those that have been completely saponified, and an average degree of polymerization of 200 to 5000, preferably 500 to 4000, from the viewpoint of improving film formation and film brittleness. Is used. Examples of the cation-modified polyvinyl alcohol include primary to tertiary amino groups and quaternary ammonium groups as described in JP-A No. 61-10383, for example, in the main chain or side chain of polyvinyl alcohol. It has polyvinyl alcohol.

  The content of polyvinyl alcohol in the coating solution is preferably from 3 to 35 mass%, more preferably from 5 to 30 mass%, based on the inorganic fine particles. Moreover, although other hydrophilic binders can be used in combination, it is preferably 20% by mass or less with respect to polyvinyl alcohol.

  In the present invention, auxiliary binders other than polyvinyl alcohol can be added. Examples of auxiliary binders include gelatin and its modified products, lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, and gelatin derivatives such as gelatin reacted with dibasic acid anhydrides such as phthalic acid, maleic acid, and fumaric acid. Gelatin, oxidized starch, cationized starch, starch such as etherified starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, polyvinylpyrrolidone, polyvinylpyridium halide, polyacrylic acid soda, acrylic acid methacrylic acid copolymer salt, Polyethylene glycol, polypropylene glycol, polyvinyl ether, alkyl vinyl ether / maleic anhydride copolymer, styrene / maleic anhydride copolymer and their salts, synthetic polymers such as polyethyleneimine, styrene / butane Enene copolymer, conjugated diene copolymer latex such as methyl methacrylate / butadiene copolymer, polyvinyl acetate, vinyl acetate / maleic acid ester copolymer, vinyl acetate / acrylic acid ester copolymer, ethylene / vinyl acetate Acrylic polymer or copolymer such as vinyl acetate polymer latex such as copolymer, acrylic acid ester polymer, methacrylic acid ester polymer, ethylene / acrylic acid ester copolymer, styrene / acrylic acid ester copolymer Polymer latex, vinylidene chloride copolymer latex, etc. or functional group-modified polymer latex with functional group-containing monomers such as carboxyl groups of these polymers, thermosetting synthetic resin systems such as melamine resin, urea resin, etc. Water-based adhesive and polymethyl methacrylate, unsaturated polyester resin Vinyl acetate copolymers chloride, polyvinyl butyral, can be mentioned synthetic resin adhesive such as alkyd resins, it may be contained singly or in combination.

  In addition to various inorganic acids, organic acids, ink fixing agents, cross-linking boron, zirconium, and titanium-containing compounds, image preservatives, colorants, thickeners, aqueous dispersions in the present invention A surfactant or the like can be added as appropriate.

As the support in the present invention, resin coated paper, high quality paper, medium quality paper, coated paper for printing, synthetic paper, and the like can be used. The thickness of the support in the present invention is not particularly limited, but is preferably in the range of 30 to 300 μm. The coating amount of the ink receiving layer is preferably ³ to 40 g / m ² , and the coating amount of the upper layer is preferably 0.2 to 15 g / m ² .

  In the present invention, as a drying device for the applied coating liquid, a linear tunnel dryer, an arch dryer, an air loop dryer, a hot air dryer such as a sine curve air float dryer, a dryer using an infrared ray, a heated dryer, a microwave, etc. And various other drying apparatuses.

  In the following, the present invention will be described in detail by way of examples. Needless to say, the present invention is not limited to the examples. Moreover, addition amount% is the mass%, and the number of addition parts is the addition amount of solid content mass conversion.

<Preparation of aqueous dispersion 1>
Water was added to the following formulation to adjust the concentration to obtain an aqueous dispersion 1 having a solid concentration of 16% by mass.
Alumina hydrate (manufactured by Sasol, Disperal HP14): 100 parts polyvinyl alcohol (manufactured by Kuraray, PVA235): 7 parts amidosulfuric acid: 0.8 part borax: 0.1 part amphoteric surfactant (manufactured by Nippon Surfactant) , SWAM AM-2150): 0.3 parts

<Preparation of aqueous dispersion 2>
After adding 2.5 parts of dimethyldiallylammonium chloride homopolymer (molecular weight 9,000) and 100 parts of gas phase method silica (average primary particle diameter 7 nm, specific surface area 300 m ² / g) to water to prepare a preliminary dispersion, A silica dispersion 1 having a solid content concentration of 20% by mass was produced by passing twice with a high-pressure homogenizer under a pressure of 30 MPa.

The concentration was adjusted by adding water to the following composition to obtain an aqueous dispersion 2 having a solid content concentration of 14% by mass.
Silica dispersion 1: 100 parts polyvinyl alcohol (manufactured by Kuraray Co., PVA235): 20 parts boric acid: 2 parts basic polyaluminum hydroxide (manufactured by Riken Green, Purachem WT): 3 parts amphoteric surfactant (Nippon Surfactant) Manufactured by SWAM AM-2150): 0.3 parts

<Preparation of aqueous dispersion 3>
Precipitation method silica (Nipseal LP; average primary particle size 15 nm, average secondary particle size 15 μm, BET specific surface area 203 m ² / g) manufactured by Tosoh Silica Co., Ltd. was used as the wet method silica. After adding 3 parts of dimethyldiallylammonium chloride homopolymer (molecular weight 9,000) and wet silica to water and stirring vigorously with a biaxial dissolver (circumferential speed 10 m / s) to prepare a preliminary dispersion, NanoGlen mill (Asada Made by Iron Works; internal volume 20 l, 0.3 mm zirconia beads with an apparent bulk volume ratio of 76.5% filled) were wet pulverized under the operating conditions of disk peripheral speed 14 m / s and liquid flow rate 6 l / min. A silica dispersion 2 having a solid content concentration of 30% by mass was prepared.

The concentration was adjusted by adding water to the following composition to obtain an aqueous dispersion 3 having a solid content concentration of 17% by mass.
Silica dispersion 2: 100 parts polyvinyl alcohol (PVA235 manufactured by Kuraray Co., Ltd.): 15
Boric acid: 3 parts amphoteric surfactant (manufactured by Nippon Surfactant, SWAM AM-2150): 0.3 parts

<Crosslinking agent solution 1>
The crosslinking agent liquid 1 was prepared with the following formulation.
Water: 93 parts Boric acid: 3 parts Borax: 4 parts

<Crosslinking agent solution 2>
A raw material of zirconium acetate (ZA30, manufactured by Daiichi Rare Element Industries) was used as a crosslinking agent liquid 2.

<Crosslinking agent solution 3>
A solution obtained by diluting titanium triethanolamate (TC-400, manufactured by Matsumoto Fine Chemical Co., Ltd.) twice with water was used as a crosslinking agent solution 3.

Example 1
From a two-fluid nozzle installed using a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 13 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 1 = 21: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was.

(Example 2)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 2 each facing the support surface with the spray center axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 13 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 2 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 2 = 16: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

Example 3
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 3 each facing the support surface with the spray central axis of the nozzle set at 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 13 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 3 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 3 = 14: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

Example 4
From a two-fluid nozzle installed using a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 35 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 1 = 21: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was.

(Example 5)
From a two-fluid nozzle installed using a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 277 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 1 = 21: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was.

(Example 6)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 2 each facing the support surface with the spray center axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 281 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 2 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 2 = 16: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

(Example 7)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 3 each facing the support surface with the spray central axis of the nozzle set at 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 274 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 3 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 3 = 14: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

(Example 8)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 2 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 37 μm. The mixing ratio of the aqueous dispersion 2 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 2: crosslinking agent liquid 1 = 17: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

Example 9
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² and a water dispersion 3 and a crosslinking agent liquid 1 facing each other with the spray central axis of the nozzle at 45 ° with respect to the support surface. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 37 μm. The mixing ratio of the aqueous dispersion 3 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 3: crosslinking agent liquid 1 = 19: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was.

(Example 10)
From a two-fluid nozzle installed using a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 13 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 1 = 21: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was. Further, the aqueous dispersion 1 was applied as an upper layer using a curtain coating apparatus. The solid coating amount of the upper layer was 9 g / m ² , and the total coating amount was 21 g / m ² .

(Example 11)
Using a high-quality paper having a basis weight of 165 g / m ² as a support, the aqueous dispersion 2 and the crosslinking agent liquid 1 are sprayed from a two-fluid nozzle installed on the support surface with the jet central axis facing the 45 ° angle. And applied to the support. The average droplet diameter at the position where both liquids were mixed was 37 μm. The mixing ratio of the aqueous dispersion 2 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 2: crosslinking agent liquid 1 = 17: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was. Further, the aqueous dispersion 1 was applied as an upper layer using a curtain coating apparatus. The solid coating amount of the upper layer was 9 g / m ² , and the total coating amount was 21 g / m ² .

(Example 12)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² and a water dispersion 3 and a crosslinking agent liquid 1 facing each other with the spray central axis of the nozzle at 45 ° with respect to the support surface. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 13 μm. The mixing ratio of the aqueous dispersion 3 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 3: crosslinking agent liquid 1 = 19: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was. Further, the aqueous dispersion 1 was applied as an upper layer using a curtain coating apparatus. The solid coating amount of the upper layer was 9 g / m ² , and the total coating amount was 21 g / m ² .

(Example 13)
From a two-fluid nozzle installed using a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 13 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 1 = 21: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was. Further, the aqueous dispersion 2 was applied as an upper layer using a curtain coating apparatus. The solid coating amount of the upper layer was 9 g / m ² , and the total coating amount was 21 g / m ² .

(Comparative Example 1)
From a two-fluid nozzle installed using a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 8.2 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 1 = 21: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was.

(Comparative Example 2)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 2 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 8.5 μm. The mixing ratio of the aqueous dispersion 2 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 2: crosslinking agent liquid 1 = 17: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

(Comparative Example 3)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² and a water dispersion 3 and a crosslinking agent liquid 1 facing each other with the spray central axis of the nozzle at 45 ° with respect to the support surface. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 7.9 μm. The mixing ratio of the aqueous dispersion 3 and the crosslinking agent solution 1, in terms of solid content, an aqueous dispersion 3: crosslinking agent solution 1 = 19: 1, and the solid content coating amount of the ink receiving layer is 12 g / m ² met It was.

(Comparative Example 4)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 2 each facing the support surface with the spray center axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 8.2 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 2 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 2 = 16: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

(Comparative Example 5)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 3 each facing the support surface with the spray central axis of the nozzle set at 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 8.2 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 3 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 3 = 14: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

(Comparative Example 6)
From a two-fluid nozzle installed using a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 324 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 1 = 21: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was.

(Comparative Example 7)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 2 and the cross-linking agent liquid 1 each facing the support surface with the spray central axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 330 μm. The mixing ratio of the aqueous dispersion 2 with a crosslinking agent solution 1, in terms of solid content, an aqueous dispersion 2: crosslinking agent solution 1 = 17: 1, and the solid content coating amount of the ink receiving layer is 12 g / m ² met It was.

(Comparative Example 8)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² and a water dispersion 3 and a crosslinking agent liquid 1 facing each other with the spray central axis of the nozzle at 45 ° with respect to the support surface. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 332 μm. The mixing ratio of the aqueous dispersion 3 and the crosslinking agent liquid 1 was, in terms of solid content, aqueous dispersion 3: crosslinking agent liquid 1 = 19: 1, and the solid content coating amount as an ink receiving layer was 12 g / m ^2. It was.

(Comparative Example 9)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 2 each facing the support surface with the spray center axis of the nozzle being 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 324 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 2 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 2 = 16: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

(Comparative Example 10)
From a two-fluid nozzle installed with a high-quality paper having a basis weight of 165 g / m ² as a support, and the water dispersion 1 and the cross-linking agent liquid 3 each facing the support surface with the spray central axis of the nozzle set at 45 °. Sprayed and applied to the support. The average diameter of the sprayed droplets at this time was 324 μm. The mixing ratio of the aqueous dispersion 1 and the crosslinking agent liquid 3 was, in terms of solid content, aqueous dispersion 1: crosslinking agent liquid 3 = 14: 1, and the solid content coating amount as the ink receiving layer was 12 g / m ^2. It was.

(Comparative Example 11)
A fine paper having a basis weight of 165 g / m ² was used as a support, and the aqueous dispersion 1 was sprayed perpendicularly to the support surface with respect to the support surface and applied to the support. The average diameter of the sprayed droplets at this time was 35 μm. The solid coating amount as the ink receiving layer was 12 g / m ² .

(Comparative Example 12)
A fine paper having a basis weight of 165 g / m ² was used as a support, and the aqueous dispersion 2 was sprayed perpendicularly to the support surface with respect to the support surface and applied to the support. The average diameter of the sprayed droplets at this time was 37 μm. The solid coating amount as the ink receiving layer was 12 g / m ² .

(Comparative Example 13)
A fine paper having a basis weight of 165 g / m ² was used as a support, and the aqueous dispersion 3 was sprayed perpendicularly to the support surface with respect to the support surface and applied to the support. The average diameter of the sprayed droplets at this time was 37 μm. The solid coating amount as the ink receiving layer was 12 g / m ² .

(Comparative Example 14)
A fine paper having a basis weight of 165 g / m ² was used as a support, and the aqueous dispersion 1 was sprayed perpendicularly to the support surface with respect to the support surface and applied to the support. The average diameter of the sprayed droplets at this time was 35 μm. The solid coating amount as the ink receiving layer was 12 g / m ² . Further, the aqueous dispersion 1 was applied as an upper layer using a curtain coating apparatus. The solid coating amount of the upper layer was 9 g / m ² , and the total coating amount was 21 g / m ² .

(Comparative Example 15)
The cross-linker liquid 1 was applied to the support with an air knife coating apparatus using a high-quality paper having a basis weight of 165 g / m ² as the support. The amount of the crosslinking agent applied was 1.2 g / m ² . Further, the aqueous dispersion 1 was applied using an ink receiving layer using a curtain coating apparatus. The solid coating amount of the ink receiving layer was 12 g / m ² , and the total coating amount was 13.2 g / m ² .

(Comparative Example 16)
The high-quality paper having a basis weight of 165 g / m ² was used as a support, and the crosslinking agent liquid 2 was applied to the support using an air knife coating device. The amount of the crosslinking agent applied was 1.1 g / m ² . Further, the aqueous dispersion 1 was applied using an ink receiving layer using a curtain coating apparatus. The solid coating amount of the ink receiving layer is 12 g / ^{m 2,} the coating amount of the total became 13.1 g / ^{m 2.}

(Comparative Example 17)
The high-quality paper having a basis weight of 165 g / m ² was used as a support, and the crosslinking agent liquid 3 was applied to the support using an air knife coating device. The amount of the crosslinking agent applied was 1.4 g / m ² . Further, the aqueous dispersion 1 was applied using an ink receiving layer using a curtain coating apparatus. The solid coating amount of the ink receiving layer is 12 g / ^{m 2,} the coating amount of the total became 13.4 g / ^{m 2.}

(Comparative Example 18)
The cross-linker liquid 1 was coated on a support with an air knife coating device using a high-quality paper having a basis weight of 165 g / m ² as the support. The amount of the crosslinking agent applied was 1.2 g / m ² . Further, the aqueous dispersion 2 was applied as an ink receiving layer using a curtain coating apparatus. The solid coating amount of the ink receiving layer was 12 g / m ² , and the total coating amount was 13.2 g / m ² .

(Comparative Example 19)
The cross-linker liquid 1 was applied to the support with an air knife coating apparatus using a high-quality paper having a basis weight of 165 g / m ² as the support. The amount of the crosslinking agent applied was 1.2 g / m ² . Further, the aqueous dispersion 3 was applied as an ink receiving layer using a curtain coating apparatus. The solid coating amount of the ink receiving layer was 12 g / m ² , and the total coating amount was 13.2 g / m ² .

<Evaluation>
The ink jet recording materials obtained in Examples 1 to 13 and Comparative Examples 1 to 19 were evaluated as follows.

(appearance)
The appearance of the recording material was visually evaluated according to the following evaluation criteria.
○: Uniform glossiness and no unevenness of the coating layer is observed.
(Triangle | delta): The gloss unevenness and the unevenness | corrugation of a coating layer of a level which are satisfactory as a product are observed.
X: Gloss unevenness and unevenness of the coating layer at a level where the product is not possible are observed.

(Coating layer cracks)
Printing was performed with a MAXART PX-5600 manufactured by Seiko Epson Corporation, and the solid portion of cyan was magnified with a microscope and visually evaluated. The evaluation criteria are as follows.
◯: A good state in which cracks are not generated and density unevenness in printing is not observed.
(Triangle | delta): A crack generate | occur | produces slightly, a density nonuniformity is seen partially, and it has influence on the reproducibility of an image.
X: Cracks are generated on the entire surface, density unevenness is large, and image reproducibility is significantly impaired.

(Print density)
Printing was performed with a MAXART PX-5600 manufactured by Seiko Epson, and the maximum density of the four colors of CMYK was measured with SpectroEye of Gretag Macbeth. The color development was determined according to the following criteria based on the total density of the four colors.
A: 7.5 or more.
○: 7.0 or more and less than 7.5.
(Triangle | delta): 6.5 or more and less than 7.0.
X: Less than 6.5.

  The evaluation results are shown in Table 1. As shown in the present invention, at least one surface on the support is made of one or more compounds containing boron, zirconium, and titanium having a function of cross-linking polyvinyl alcohol with an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol. The aqueous dispersion of the selected cross-linking agent is finely atomized and mixed using a two-fluid nozzle so that the average particle diameter is in the range of 10 to 300 μm, and is applied onto the support, so that the appearance is excellent. There is no generation of cracks in the layer, and an ink jet recording material having a high printing density is obtained. In addition, the surface of the obtained inkjet recording material is coated with an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol using a curtain coating device, so that the appearance is excellent and cracks in the coating layer occur. Therefore, an ink jet recording material having a higher printing density can be obtained.

Claims (4)

  One or more cross-linking agents selected from compounds containing boron, zirconium, and titanium having an action of cross-linking polyvinyl alcohol and an aqueous dispersion containing inorganic fine particles and polyvinyl alcohol as main components on at least one surface of the support. An ink jet recording material, wherein an aqueous dispersion is atomized into an average particle diameter of 10 to 300 μm, sprayed, mixed and applied to a support.   One or more cross-linking agents selected from compounds containing boron, zirconium, and titanium having an action of cross-linking polyvinyl alcohol and an aqueous dispersion containing inorganic fine particles and polyvinyl alcohol as main components on at least one surface of the support. A method for producing an ink jet recording material, wherein an aqueous dispersion is atomized into a range of an average particle diameter of 10 to 300 μm using a two-fluid nozzle, sprayed, mixed, and coated on a support.   2. The ink jet recording material according to claim 1, wherein an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol is applied to the application surface of the ink jet recording material using a curtain coating device.   3. The method for producing an ink jet recording material according to claim 2, further comprising a step of applying an aqueous dispersion mainly composed of inorganic fine particles and polyvinyl alcohol on a surface to which the ink jet recording material is applied using a curtain coating apparatus.

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