JP2012171224A - Inkjet recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet recording material which has high ink absorbency, reduced ink bleeding and high glossiness, namely, jointly has high ink absorbency, high glossiness and high ink bleeding resistance.SOLUTION: In the inkjet recording material having an ink receiving layer essentially consisting of inorganic fine particles with the average secondary particle diameter of ≤500 nm on a non-water absorbent support, inorganic fine particles with the secondary average particle diameter of 1 to 20 μm dispersed in the presence of cationic emulsion are incorporated into the ink receiving layer.

Description

  The present invention contains inorganic fine particles having an average secondary particle diameter of 500 nm or less on a non-water-absorbing support and inorganic fine particles having an average secondary particle diameter of 1 to 20 μm dispersed in the presence of a cationic emulsion. To provide an ink jet recording material having high ink absorbability, low ink bleeding, and high glossiness, so-called high ink absorbability, high gloss, and high ink bleeding resistance. is there.

  In recent years, the ink jet recording technology has been remarkably improved, and recently, the ink jet recording system has been widely used for high-quality output such as photographs. The quality of the recording material is also very important for such high-quality output. Especially in the case of photographic output, as a recording material having high gloss and high ink absorptivity similar to silver salt photography, A recording material in which a porous ink receiving layer mainly containing an inorganic pigment is provided on a support such as a resin film is widely known and used.

  As such a recording material, for example, JP-B-3-56552, JP-A-10-119423, JP-A-2000-21235, JP-A-2000-309157 and the like disclose a vapor phase method as an inorganic pigment. Examples using silica are disclosed in JP-A-9-286165, JP-A-10-181190, etc., respectively, using precipitated silica. In these recording materials using inorganic pigments, excellent ink absorption is achieved by utilizing voids formed of porous pigments while obtaining high gloss by atomizing the pigments.

  In recent years, inkjet printers have been devised for higher quality, one is increasing the printing speed, and the other is decreasing the size of ink droplets to achieve high color development. . In order to cope with this higher printing speed and smaller ink droplets, the ink jet recording material is always required to have higher ink absorbency than ever before. At the same time, the ink jet recording material is also required to have a gloss as high as that of a silver salt photograph.

  Japanese Patent Application Laid-Open No. 2003-291514 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2004-1449 (Patent Document 2) disclose the use of inorganic pigments having different particle diameters to improve ink absorbability. However, although ink absorptivity is improved, all of them are descriptions relating to a proofreading ink-jet recording material and are not intended to have a gloss as high as that of a silver salt photograph.

  Another improvement in the quality of inkjet printers is to improve fastness such as light resistance, ozone resistance, and water resistance. Of these, improvement in light resistance and ozone resistance has been greatly improved since it is required for both ink and ink jet recording materials of ink jet printers. On the other hand, the improvement in ink bleeding under water resistance, particularly in a high humidity environment, is largely due to improvements in the ink jet recording material.

  Japanese Patent Application Laid-Open No. 2004-58575 (Patent Document 3) discloses an ink jet recording material in which a layer containing a cationic emulsion is provided below an ink receiving layer. Although it is a technique for improving the adhesion between the ink receiving layer and the ink receiving layer, the bleeding that occurs in a high humidity environment is still at an insufficient level and needs to be improved.

  Japanese Patent Application Laid-Open No. 2006-248017 (Patent Document 4) discloses an ink jet recording material containing a cationic emulsion in an ink receiving layer separated from a support, which is highly improved in bleeding in a high humidity environment. Although described as having ink absorptivity, the level of ink absorptivity currently required for inkjet recording materials is not sufficient and needs improvement.

JP 2003-291514 A JP 2004-1449 A JP 2004-58575 A JP 2006-2448017 A

  An object of the present invention is to provide an ink jet recording material that has high ink absorbability, low ink bleeding, and high glossiness, which combines so-called high ink absorption, high gloss, and high ink bleeding resistance. is there.

  As a result of intensive studies, it has been found that the above object of the present invention can be achieved by the following means.

  1) In an ink jet recording material having an ink receiving layer mainly composed of inorganic fine particles having an average secondary particle diameter of 500 nm or less on a non-water-absorbing support, the ink receiving layer was dispersed in the presence of a cationic emulsion. An ink jet recording material comprising inorganic fine particles having an average secondary particle diameter of 1 to 20 μm.

  2) Inorganic fine particles with a solid content ratio of the inorganic fine particles having an average secondary particle diameter of 500 nm or less and the inorganic fine particles having an average secondary particle diameter of 1 to 20 μm in a mass ratio of 500 nm or less: 1-20 μm inorganic fine particles = 99 The inkjet recording material according to 1), wherein the inkjet recording material is 1 to 80:20.

  3) The solid content ratio of the cationic emulsion to inorganic fine particles having an average secondary particle diameter of 1 to 20 μm is a cationic emulsion: 1 to 20 μm inorganic fine particles = 60: 40 to 10:90 in mass ratio. The ink jet recording material according to 1) or 2), which is characterized in that

  According to the present invention, it is possible to provide an ink jet recording material having high ink absorbability, high glossiness and high ink bleeding resistance.

Hereinafter, the ink jet recording material of the present invention will be described in detail.
The cationic emulsion used in the present invention is a cationic or cationically modified aqueous emulsion, for example, a conjugated diene copolymer emulsion such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer; Acrylic polymer emulsions such as acrylic acid and methacrylic acid ester polymers or copolymers, acrylic acid and methacrylic acid polymers or copolymers; styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers Styrene-acrylic polymer emulsions such as polymers; vinyl polymer emulsions such as ethylene vinyl acetate copolymers, urethane emulsions having urethane bonds, etc. that are cationized using cationic groups, cationic surfactants Emalsi That the emission surface is cationized, such as those obtained by distributing the polyvinyl alcohol to the polymerized emulsion surface under cationic polyvinyl alcohol. Among these cationic emulsions, cationic emulsions whose main component is styrene-acrylic polymer particles are preferred.

  In the presence of the cationic emulsion, inorganic fine particles having an average secondary particle diameter of 1 to 20 μm are dispersed. The solid content ratio of the cationic emulsion and the inorganic fine particles having an average secondary particle diameter of 1 to 20 μm is mass. Cationic emulsion: 1 to 20 μm inorganic fine particles = 60: 40 to 10:90 is preferable, and cationic emulsion: 1 to 20 μm inorganic fine particles = 40: 60 to 20:80 is more preferable.

  In the present invention, when the solid content ratio between the cationic emulsion and the inorganic fine particles having an average secondary particle size of 1 to 20 μm is excessively larger than the above ratio, the ink absorbency effect is gradually reduced. When the number of inorganic fine particles having an average secondary particle diameter of 1 to 20 μm is excessively larger than the above ratio, the glossiness gradually decreases.

  The inorganic fine particles in the ink receiving layer in the present invention will be described.

  The ink receiving layer of the present invention contains an inorganic pigment having an average secondary particle diameter of 500 nm or less. Such inorganic pigments include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, titanium dioxide, zinc oxide, zinc hydroxide, calcium silicate, magnesium silicate, amorphous synthetic silica, alumina, alumina hydrate, water Examples include magnesium oxide. Among these, amorphous synthetic silica, alumina, and alumina hydrate are particularly preferable. Amorphous synthetic silica can be roughly classified into wet method silica and gas phase method silica depending on the production method. Vapor phase silica is also called a dry method as opposed to a wet method, 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 in silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state. Vapor phase silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd.

The vapor phase silica that can be used in the present invention will be described. The average primary particle diameter of the vapor phase silica used in the present invention is preferably 30 nm or less, and preferably 15 nm or less in order to obtain higher gloss. Further, those having an average primary particle diameter of 3 to 15 nm and a specific surface area by the BET method of 200 m ² / g or more (preferably 250 to 500 m ² / g) are particularly preferable. The average primary particle diameter as used in the present invention is an average value obtained by observing the diameter of a circle equal to the projected area of each of the 100 primary particles existing within a certain area by observation with a microscopic electron microscope. The BET method is a method for measuring the surface area of a powder by a vapor phase adsorption method, and is a method for obtaining the total surface area, that is, the specific surface area of a 1 g sample from an adsorption isotherm. Usually, nitrogen gas is often used as the adsorbed gas, and the most frequently used method is to measure the amount of adsorption from the change in pressure or volume of the gas to be adsorbed. The most prominent expression for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, and Teller equation, called the BET equation, which is widely used for determining the surface area. The adsorption amount is obtained based on the BET equation, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.

  The average secondary particle size of the vapor phase method silica is 500 nm or less, more preferably 10 to 300 nm. In order to make the average secondary particle diameter of the gas phase method silica not more than 500 nm, the gas phase method silica and the dispersion medium are premixed by ordinary propeller stirring, turbine type stirring, homomixer type stirring, etc., and then a ball mill, It is preferable to perform dispersion using a media mill such as a bead mill or a sand grinder, a pressure disperser such as a high-pressure homogenizer or an ultra-high pressure homogenizer, or an ultrasonic disperser. The dispersion treatment is performed in the presence of a cationic polymer. It is preferable to disperse. The average secondary particle diameter in the present invention is obtained by measuring a dilute dispersion with a laser diffraction / scattering particle size distribution analyzer.

  Examples of the cationic polymer used for the dispersion of the vapor phase silica include polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, JP-A-59-33176, JP JP 59-33177, JP 59-1555088, JP 60-11389, JP 60-49990, JP 60-83882, JP 60-109894. JP, 62-198493, JP 63-49478, JP 63-115780, JP 63-280681, JP 1-40371, JP 6-6 No. 234268, JP-A-7-125411, JP-A-10-19376, and the like. Polymers having Moniumu base is preferably used. In particular, diallylamine derivatives are preferably used as the cationic polymer. In terms of dispersibility and dispersion viscosity, the molecular weight of these cationic polymers is preferably about 2000 to 100,000, and more preferably about 2000 to 30,000. The amount of the cationic polymer used is preferably in the range of 1 to 10% by weight relative to the vapor phase silica.

  As the inorganic pigment contained in the ink receiving layer of the present invention, alumina or alumina hydrate is also preferably used. Alumina or alumina hydrate is aluminum oxide or its hydrate, which may be crystalline or amorphous, and has an amorphous shape, a spherical shape, a plate shape, or the like. Either of them may be used or may be used in combination.

As the alumina oxide that can be used in the present invention, γ-alumina, which is a γ-type crystal of aluminum oxide, is preferable, and δ group crystal is particularly preferable. The alumina hydrate that can be used in the present invention is represented by a constitutional formula of Al ₂ O ₃ .nH ₂ O (n = 1 to 3). The hydrated aluminum oxide can be obtained by a known production method such as hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali, hydrolysis of aluminate, and the like. The average secondary particle diameter of the alumina hydrate used in the present invention is 500 nm or less, preferably 10 to 300 nm.

In order to stabilize the dispersion of alumina or alumina hydrate used in the present invention, various acids can be added as a sol peptizer or a dispersant of alumina or alumina hydrate powder. Known acids can be used for sol peptization, for example, inorganic acids such as nitric acid, hydrochloric acid and hydrobromic acid, organic acids having a carboxylic acid group such as acetic acid, lactic acid and formic acid, or Examples thereof include organic acids having a sulfonic acid group such as methanesulfonic acid and p-toluenesulfonic acid. These may use different acids for each of the plurality of ink receiving layer coating solutions, or two or more of them may be used in combination in one coating solution. The amount of acid added is preferably 8 to 120 mmol, more preferably 10 to 50 mmol, based on 100 g of alumina hydrate in terms of Al ₂ O ₃ .

  The inorganic fine particles having an average secondary particle diameter of 1 to 20 μm used in the present invention will be described. As the inorganic fine particles, diatomaceous earth, clay, calcined clay, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium dioxide, titanium dioxide-coated mica, barium sulfate, molybdenum white, zinc white, lithopone, Zinc sulfide, gypsum, lead white, calcium sulfate, zinc oxide, zinc hydroxide, zinc carbonate, hydrotalcite, aluminum silicate, calcium silicate, magnesium silicate, aluminum hydroxide, zeolite, magnesium hydroxide, titanium oxide, amorphous Synthetic silica, glass powder, barium sulfate and the like can be mentioned, and amorphous synthetic silica, especially wet method silica, is particularly preferably used from the viewpoint of absorbability.

  Wet method silica is further classified into precipitation method silica, gel method silica, and sol method silica 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 silica produced by this method become loosely agglomerated particles, and particles that are relatively easy to grind are obtained. Precipitated silica is commercially available, for example, as a nip seal from Tosoh Silica Co., Ltd., as a Toku Seal from Tokuyama Co., Ltd., and as a fine seal. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. During the ripening, the fine particles dissolve and reprecipitate so as to bind other primary particles, so that the distinct primary particles disappear and form relatively hard aggregated particles having an internal void structure. For example, commercially available as Toyo Silica Co., Ltd. as nip gel, from Mizusawa Chemical Industry Co., Ltd. as Mizukasil, from Grace Japan Co., Ltd. as syloid and silo jet. The sol silica is also called colloidal silica, and is obtained by heating and aging a silica sol obtained through metathesis of sodium silicate acid or through an ion exchange resin layer. For example, it is commercially available as Snowtex from Nissan Chemical Industries, Ltd. Yes.

  In the present invention, among the wet method silica, precipitation method silica and gel method silica can be preferably used, and more preferably gel method silica can be used.

  A method for dispersing inorganic fine particles having an average secondary particle diameter of 1 to 20 μm used in the present invention will be described. As a dispersion method, it can disperse | distribute by the well-known normal propeller stirring, turbine type stirring, a homomixer stirring, etc.

  The ink receiving layer of the present invention mainly contains inorganic fine particles having an average secondary particle diameter of 500 nm or less. Here, the main content is 60 mass% with respect to the total solid content constituting the ink receiving layer. It is contained above, Preferably it is containing 65 mass% or more, More preferably, it is containing 70 mass% or more.

  In the present invention, the ink receiving layer contains inorganic fine particles having an average secondary particle diameter of 500 nm or less and inorganic fine particles having an average secondary particle diameter of 1 to 20 μm. Inorganic fine particles having a particle diameter of 500 nm or less: Inorganic fine particles having an average secondary particle diameter of 1 to 20 μm = 99: 1 to 80:20, more preferably, inorganic fine particles having an average secondary particle diameter of 500 nm or less: Inorganic fine particles having a secondary particle size of 1 to 20 μm = 97: 3 to 90:10.

  The ink receiving layer of the present invention preferably contains a hydrophilic binder in order to maintain the properties as a film and to obtain high transparency and high ink permeability. As such a hydrophilic binder, polyvinyl alcohol, polyethylene glycol, starch, dextrin, carboxymethyl cellulose, polyvinyl pyrrolidone, polyacrylic acid ester and derivatives thereof are used. Particularly preferred hydrophilic binders are completely or partially saponified. Polyvinyl alcohol. Particularly preferred among the polyvinyl alcohols are those having a degree of saponification of 80% or more or those completely saponified. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferable.

  Examples of the polyvinyl alcohol include cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, and other polyvinyl alcohol derivatives in addition to general polyvinyl alcohol. Polyvinyl alcohol may be used alone or in combination of two or more.

  The content of polyvinyl alcohol in the ink-receiving layer coating liquid of the present invention is preferably 3 to 30% by mass, particularly preferably 5 to 25% by mass with respect to the inorganic pigment having an average secondary particle size of 500 nm or less.

The solid content coating amount of the ink receiving layer in the invention is preferably 10 to 60 g / m ² . The solid content concentration of the ink receiving layer coating liquid is preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass.

  The ink receiving layer of the present invention preferably contains a crosslinking agent together with a hydrophilic binder. As the crosslinking agent, known crosslinking agents can be used. Specific examples 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, US Pat. No. 3,635,718 Compounds having reactive olefins as described in the specification, N-methylol compounds as described in US Pat. No. 2,732,316, isocyanates as described in US Pat. No. 3,103,437, Aziridination as described in US Pat. No. 3,017,280 and US Pat. No. 2,983,611 Carbodiimide compounds as described in US Pat. No. 3,100,704, epoxy compounds as described in US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid, dihydroxydioxane Inorganic cross-linking agents such as dioxane derivatives such as, chromium alum, zirconium sulfate, boric acid, borates, and borax. In the present invention, boric acid or borate is preferable. Examples of the boric acid used in the present invention include orthoboric acid, metaboric acid, and hypoboric acid, and examples of the borate include sodium salts, potassium salts, and ammonium salts thereof. 0.1-40 mass% is preferable with respect to the hydrophilic binder contained in each layer, and, as for the addition amount of a crosslinking agent, 0.5-30 mass% is more preferable.

  The ink receiving layer of the present invention may contain a water-soluble polyvalent metal compound in order to improve water resistance. As the water-soluble polyvalent metal compound, a water-soluble aluminum compound and a water-soluble zirconium compound can be preferably used.

  Examples of the water-soluble zirconium compound used in the present invention include zirconium acetate, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, zirconium carbonate / ammonium, zirconium carbonate / potassium, zirconium sulfate, zirconium fluoride, zirconium chloride, zirconium chloride octahydrate. Examples thereof include a hydrate, zirconium oxychloride, and hydroxyzirconium chloride. Among these water-soluble zirconium compounds, zirconium acetate (zirconyl acetate) and zirconium oxychloride are particularly preferable.

  As the water-soluble aluminum compound, for example, as the inorganic salt, aluminum chloride or its hydrate, aluminum sulfate or its hydrate, ammonium alum and the like are known. Furthermore, a basic polyaluminum hydroxide compound which is an inorganic aluminum-containing cationic polymer is known.

Among these water-soluble aluminum compounds, those that can be stably added to the coating solution for forming the ink receiving layer are preferable, and a basic polyaluminum hydroxide compound is preferably used. The main component of this compound is represented by the following formula 1, 2 or 3, for example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ⁴⁺ , [Al ₁₃ (OH) ₃₄ ] ⁵⁺ , It is a water-soluble polyaluminum hydroxide that stably contains a basic and high-molecular polynuclear condensed ion such as [Al ₂₁ (OH) ₆₀ ] ³⁺ .

[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 in the name of polyaluminum chloride (PAC) from Taki Chemical Co., Ltd., in the name of polyaluminum hydroxide (Paho) from Asada Chemical Industry Co., Ltd., and Riken Co., Ltd. It is commercially available from Green under the name of Purachem WT and from other manufacturers for the same purpose, and various grades are readily available. In the present invention, these commercially available products can be used as they are.

  The content of the water-soluble polyvalent metal compound is preferably in the range of 0.1 to 10% by mass with respect to the inorganic pigment contained in the ink receiving layer.

  For the ink receiving layer, various known additives such as coloring dyes, coloring pigments, ultraviolet absorbers, antioxidants, antifoaming agents, leveling agents, preservatives, fluorescent brighteners, viscosity stabilizers, pH regulators, etc. Can also be added. Further, the pH of the coating solution for the ink receiving layer of the present invention is preferably in the range of 3.3 to 6.5, particularly preferably in the range of 3.5 to 5.5.

  In addition to the ink receiving layer, the ink jet recording material of the present invention may be further provided with a layer having other functions such as an undercoat layer, a protective layer, and a gloss developing layer.

  As the non-water-absorbing support used in the present invention, polyethylene, polypropylene, polyvinyl chloride, diacetate resin, triacetate resin, cellophane, acrylic resin, polyethylene terephthalate, polyethylene naphthalate film, polyolefin resin-coated paper, etc. are used. The thickness of these supports is preferably about 50 to 300 μm.

  When using a film which is a non-water-absorbing support or an olefin resin-coated paper, activation treatment such as corona discharge treatment and flame treatment can be performed on the surface on which the ink receiving layer is provided. Furthermore, it is preferable to provide an undercoat layer mainly composed of a natural polymer compound or a synthetic resin on the surface on which the ink receiving layer is provided, and an undercoat layer mainly composed of gelatin is particularly preferable.

There is no particular restriction on the coating amount of the undercoat layer is preferably in the range of 0.005~2.0g / ^{m 2} in solid coating amount, more preferably in the range of 0.01 to 1.0 g / ^{m 2,} A range of 0.02 to 0.5 g / m ² is particularly preferred.

  Various back coat layers can be coated on the support in the present invention to prevent charging, improve transportability, prevent curling, and the like. The backcoat layer can contain an appropriate combination of inorganic and organic antistatic agents, hydrophilic binders, latexes, curing agents, pigments, surfactants and the like.

  As a coating method used for coating the ink receiving layer of the present invention, a known coating method such as an air doctor coater, a blade coater, a rod coater, a knife coater, a reverse roll coater, a bar coater, a slide bead coater, or a curtain coater is used. be able to. For simultaneous multilayer coating, a slide bead method, a curtain method, or the like is preferable. The slide bead coating method is described in JP-A-5-96223, JP-A-11-290775, JP-A-2000-33314, etc. This is a method of applying while forming a bead between them. The curtain coating method is a method in which a curtain film of a coating solution is dropped on a support and applied as described in JP-A-10-277458, JP-A-2000-176344, JP-A-2001-46938, and the like. is there.

  Examples of the present invention will be described below. In addition, a part and% show a mass part and the mass%.

Example 1
[Production of support]
A 1: 1 mixture of hardwood bleached kraft pulp (LBKP) and hardwood bleached sulfite pulp (LBSP) was beaten to 300 ml with Canadian Standard Freeness to prepare a pulp slurry. As a sizing agent, alkylketene dimer is 0.5% to pulp, polyacrylamide is 1.0% to pulp, and cationized starch is 2.0% to pulp. Polyamide epichlorohydrin resin is 0 to pulp. 0.5% added and diluted with water to give a 0.2% slurry. This slurry was made with a long paper machine to a basis weight of 170 g / m ² , dried and conditioned to obtain a polyolefin resin-coated paper base paper. A polyethylene resin composition in which 10% anatase-type titanium is uniformly dispersed in a low density polyethylene resin having a density of 0.918 g / cm ³ is melted at 320 ° C. to a paper base having a density of 35 μm. The surface (ink-receiving layer-coated surface) was formed by extrusion coating using a cooling roll that had been subjected to extrusion coating as described above and fine-roughened. Melted at similarly 320 ° C. The blend resin composition of the low density polyethylene resin 30 parts of a density 0.962 g / cm 70 parts high density polyethylene resin of ³ and a density 0.918 g / cm ³ on the other surface, the thickness Extrusion coating was carried out to a thickness of 30 μm, and extrusion coating was performed using a cooling roll that had been roughened to obtain a back surface.

After subjecting the surface of the polyolefin resin-coated paper to a high-frequency corona discharge treatment, an undercoat layer having the following composition was applied and dried so that the amount of gelatin adhered was 50 mg / m ² .
<Underlayer>
Gelatin 100 parts Sulfosuccinic acid-2-ethylhexyl ester salt 2 parts Chrome alum 10 parts

[Preparation of inkjet recording material]
On the support, the ink receiving layer coating solution 1 having the following composition was coated with a slide bead coater so that the dry coating amount of the vapor phase silica was 20.0 g / m ^2, and then at 8 ° C. for 15 seconds. It cooled, air of 30-55 degreeC was sprayed in order, and it dried and produced the inkjet recording material of Example 1. FIG.

[Preparation of vapor phase silica dispersion]
After adding 4 parts of dimethyldiallylammonium chloride homopolymer (molecular weight 9000) and 100 parts of gas phase method silica (average primary particle diameter 7 nm, specific surface area 300 m ² / g by BET method) to water to prepare a preliminary dispersion, A gas phase method silica dispersion having a solid content concentration of 20% was prepared by a homogenizer treatment. The average secondary particle diameter of the vapor phase method silica was 135 nm.

[Preparation of wet method silica dispersion 1]
50 parts by weight of a cationic emulsion (SE2220, manufactured by Seiko PMC Co., Ltd.) and water-based silica (manufactured by Mizusawa Chemical Industry Co., Ltd., P-78A) mainly composed of styrene-acrylic polymer particles in water. After adding 100 parts to prepare a preliminary dispersion, propeller stirring was performed at 700 rpm for 10 minutes to prepare a wet process silica dispersion having a solid content concentration of 10%. The average secondary particle diameter of the wet process silica was 10 μm.

<Ink-receiving layer coating solution 1>
Gas phase method silica dispersion 1 (as solid phase of gas phase method silica) 100 parts Boric acid 4 parts Polyvinyl alcohol 23 parts (saponification degree 88%, average polymerization degree 3500)
Wet method silica dispersion 1 (as solid content of wet method silica) 5 parts Solid content concentration of coating solution 12.0%

(Example 2)
An inkjet recording material of Example 2 was produced in the same manner as in Example 1 except that the wet method silica dispersion 1 of Example 1 was changed to the following wet method silica dispersion 2.

[Preparation of wet method silica dispersion 2]
A preliminary dispersion was prepared by adding 50 parts by weight of a cationic emulsion (SE2220, manufactured by Seiko PMC Co., Ltd.) and 100 parts of wet-process silica (manufactured by Mizusawa Chemical Co., Ltd., P-78D) to water. Thereafter, propeller stirring was performed at 700 rpm for 10 minutes to prepare a wet method silica dispersion having a solid content concentration of 10%. The average secondary particle diameter of the wet process silica was 15 μm.

(Example 3)
An inkjet recording material of Example 3 was produced in the same manner as in Example 1 except that the wet method silica dispersion 1 of Example 1 was changed to the following wet method silica dispersion 3.

[Preparation of wet method silica dispersion 3]
A preliminary emulsion was prepared by adding 50 parts of a cationic emulsion (SE2220, manufactured by Seiko PMC Co., Ltd.) to water and 100 parts of wet-process silica (manufactured by Mizusawa Chemical Co., Ltd., P-73). Thereafter, propeller stirring was performed at 700 rpm for 10 minutes to prepare a wet method silica dispersion having a solid content concentration of 10%. The average secondary particle diameter of the wet process silica was 6 μm.

Example 4
In the ink-receiving layer coating liquid 1 of Example 1, the same procedure as in Example 1 was performed except that the number of parts of the wet process silica dispersion 1 was changed from 5 parts to 0.5 parts as the solid content of the wet process silica. No. 4 inkjet recording material was produced.

(Example 5)
In the ink receiving layer coating liquid 1 of Example 1, the number of parts of the wet process silica dispersion 1 was changed from 5 parts to 25 parts as the solid content of the wet process silica. An ink jet recording material was prepared.

(Example 6)
An inkjet recording material of Example 6 was produced in the same manner as in Example 1 except that the wet method silica dispersion 1 of Example 1 was changed to the following wet method silica dispersion 4.

[Preparation of wet method silica dispersion 4]
A preliminary dispersion was prepared by adding 200 parts of a cationic emulsion (SE2220, manufactured by Seiko PMC Co., Ltd.) and 100 parts of wet-method silica (manufactured by Mizusawa Chemical Co., Ltd., P-78A) to water. Thereafter, propeller stirring was performed at 700 rpm for 10 minutes to prepare a wet method silica dispersion having a solid content concentration of 10%. The average secondary particle diameter of the wet process silica was 4 μm.

(Example 7)
An ink jet recording material of Example 7 was prepared in the same manner as in Example 1 except that the wet process silica dispersion liquid 1 of Example 1 was changed to the following wet process silica dispersion liquid 5.

[Preparation of wet method silica dispersion 5]
A preliminary dispersion was prepared by adding 6 parts by weight of a cationic emulsion (SE2220, manufactured by Seiko PMC Co., Ltd.) and 100 parts of wet method silica (manufactured by Mizusawa Chemical Co., Ltd., P-78A) to water. Thereafter, propeller stirring was performed at 700 rpm for 10 minutes to prepare a wet method silica dispersion having a solid content concentration of 10%. The average secondary particle diameter of the wet process silica was 8 μm.

(Example 8)
An ink jet recording material of Example 8 was produced in the same manner as in Example 1 except that the ink receiving layer coating liquid 1 of Example 1 was changed to the following ink receiving layer coating liquid 2.

<Ink-receiving layer coating solution 2>
Alumina hydrate (Alumina hydrate has an average secondary particle size of 120 nm) 100 parts
(As alumina solid content)
Boric acid 2 parts Polyvinyl alcohol 10 parts (degree of saponification 88%, average degree of polymerization 3500)
Wet method silica dispersion 1 (as solid content of wet method silica) 5 parts Solid content concentration of coating solution 20.0%

Example 9
An inkjet recording material of Example 9 was produced in the same manner as in Example 1 except that the wet method silica dispersion 1 of Example 1 was changed to the following wet method silica dispersion 6.

[Preparation of wet method silica dispersion 6]
50 parts by weight of a cationic emulsion (S-510HQ, manufactured by Sumika Chemtex Co., Ltd.) containing ethylene-vinyl acetate polymer particles as the main component in water and a wet method silica (manufactured by Mizusawa Chemical Co., Ltd.) P-78A) A preliminary dispersion was prepared by adding 100 parts, and then stirred by a propeller at 700 rpm for 10 minutes to prepare a wet method silica dispersion having a solid content concentration of 10%. The average secondary particle diameter of the wet process silica was 10 μm.

(Comparative Example 1)
An inkjet recording material of Comparative Example 1 was prepared in the same manner as in Example 1 except that the wet process silica dispersion liquid 1 of Example 1 was changed to the following wet process silica dispersion liquid 7.

[Preparation of wet method silica dispersion 7]
A preliminary dispersion was prepared by adding 50 parts of a cationic emulsion (SE2220 manufactured by Seiko PMC Co., Ltd.) to water and 100 parts of wet method silica (P-78F manufactured by Mizusawa Chemical Co., Ltd.). Thereafter, propeller stirring was performed at 700 rpm for 10 minutes to prepare a wet method silica dispersion having a solid content concentration of 10%. The average secondary particle diameter of the wet process silica was 25 μm.

(Comparative Example 2)
An inkjet recording material of Comparative Example 2 was prepared in the same manner as in Example 1 except that the wet method silica dispersion 1 of Example 1 was changed to the following wet method silica dispersion 8.

[Preparation of wet method silica dispersion 8]
A preliminary dispersion was prepared by adding 50 parts of a cationic emulsion (SE2220 manufactured by Seiko PMC Co., Ltd.) to water and 100 parts of wet method silica (P-78F manufactured by Mizusawa Chemical Co., Ltd.). Then, it grind | pulverized using the bead mill and produced the wet method silica dispersion liquid of solid content concentration 10%. The average secondary particle diameter of the wet process silica was 0.5 μm.

(Comparative Example 3)
An inkjet recording material of Comparative Example 3 was prepared in the same manner as in Example 1 except that the wet method silica dispersion 1 of Example 1 was changed to the following wet method silica dispersion 9.

[Preparation of wet method silica dispersion 9]
50 parts of cationic polymer (Sanbright KH-55, manufactured by Daiwa Chemical Industry Co., Ltd.) and 100 parts of wet silica (manufactured by Mizusawa Chemical Co., Ltd., P-78F) are added to the water for preliminary preparation. After preparing the dispersion, propeller stirring was performed at 700 rpm for 10 minutes to prepare a wet method silica dispersion having a solid concentration of 10%. The average secondary particle diameter of the wet process silica was 10 μm.

(Comparative Example 4)
An ink jet recording material of Comparative Example 4 was prepared in the same manner as in Example 1 except that the wet method silica dispersion was not added to the ink receiving layer coating liquid 1 of Example 1.

  The following evaluation was performed on each of the obtained ink jet recording materials. The results are shown in Table 1.

<Ink absorbability>
The amount of ink transferred to PPC paper by printing red, blue, green, and black solids with an inkjet printer (PIXUS iP8600, manufactured by Canon Inc.). Was visually observed. Evaluation was made according to the following criteria.
○: Not transferred.
Δ: Slight transfer but no problem.
X: Transfer is observed in the printed part, and ink absorbency is inferior.

<Ink bleeding>
After printing with an inkjet printer (PIXUS iP8600, manufactured by Canon Inc.), it was placed in an environment of 30 ° C. and 80% for 2 days, and the bleeding of the images before and after was visually observed. Evaluation was made according to the following criteria.
○: Good with almost no difference between images before and after.
(Triangle | delta): The level which a slight blur is seen but does not become a problem.
X: The difference in bleeding is very large due to the difference between the front and back images.

<Glossiness>
The glossiness of the blank paper ink-receiving layer surface was evaluated according to the following criteria.
○: The surface is flat and has a very high gloss.
Δ: The flatness of the surface is slightly low and slightly rough, but it can be said to be glossy paper.
X: The level of the flatness of the surface is remarkably low and it cannot be said to be glossy paper.

  From Table 1, the ink jet recording material of the present invention has high ink absorbability, low ink bleeding, and high glossiness, so-called high ink absorption, high glossiness, and high ink bleeding resistance. It turns out that it is material.

Claims (3)

  In an ink jet recording material having an ink receiving layer mainly composed of inorganic fine particles having an average secondary particle diameter of 500 nm or less on a non-water-absorbing support, an average second dispersed in the presence of a cationic emulsion in the ink receiving layer. An ink jet recording material comprising inorganic fine particles having a secondary particle size of 1 to 20 μm.   The solid content ratio of the inorganic fine particles having an average secondary particle diameter of 500 nm or less and the inorganic fine particles having an average secondary particle diameter of 1 to 20 μm in terms of mass ratio is 500 nm or less: 1-20 μm inorganic fine particles = 99: 1 The inkjet recording material according to claim 1, which is ˜80: 20.   The solid content ratio of the cationic emulsion to inorganic fine particles having an average secondary particle diameter of 1 to 20 μm is a cationic emulsion: 1 to 20 μm inorganic fine particles = 60: 40 to 10:90 in mass ratio. The ink jet recording material according to claim 1 or 2.