JP2003103922A - Ink jet recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high gloss ink jet recording material which is excellent in ink absorbency, print density, and coloring properties and controls the occur rence of image bleeding with the passage of time. SOLUTION: In the ink jet recording material having at least two ink receiving layers mainly comprising fine solid particles on a support, the ink receiving layer A close to the support contains a water repellent substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording material, and particularly to an ink jet recording material having high gloss, high ink absorbency, high print density, excellent color development, and excellent suppression of image bleeding over time. Regarding recording material.

[0002]

2. Description of the Related Art As a recording material used in an ink jet recording method, a pigment called amorphous silica or the like is formed on a support called ordinary paper or ink jet recording paper, and a porous material made of a water-soluble binder such as polyvinyl alcohol is used. A recording material provided with the ink absorption layer is known.

For example, JP-A-55-51583 and JP-A-5-51583.
No. 6-157, No. 57-107879, No. 57-10.
No. 7880, No. 59-230787, No. 62-160.
No. 277, No. 62-184879, No. 62-1833.
No. 82 and No. 64-11877, there are proposed recording materials obtained by coating a paper support with a silicon-containing pigment such as silica together with an aqueous binder.

Further, Japanese Patent Publication No. 3-56552 and Japanese Patent Laid-Open No. Hei 2
No. 188287, No. 8-132728, No. 10
81064, 10-119423, 10
-175365, 10-203006, 10-
217601, Doppei 11-20300, Doppei 11-
Nos. 20306 and 11-34481 disclose recording materials having high ink absorbency and gloss, which use synthetic silica fine particles produced by a vapor phase method (hereinafter referred to as vapor phase silica).

Further, image density and gloss obtained by using alumina or alumina hydrate in JP-A-62-174183, JP-A-2-276670, JP-A-5-32037, JP-A-6-199034 and the like. High recording materials are disclosed.

On the other hand, various performances required for ink jet recording materials such as ink absorbency, glossiness, print density,
As one method for simultaneously satisfying the surface strength and the like, an inkjet recording material having a plurality of constitutions of solid fine particles has been proposed.

For example, a recording material having a gloss-developing layer containing colloidal silica as an upper layer is disclosed in JP-A-3-2150.
No. 80, JP-A-7-89220, and JP-A-7-1173.
35, JP-A 2000-37944, etc., and JP-A 6-55829 discloses a structure of a silica porous layer and an alumina hydrate-containing layer, JP-A-7-8921.
Japanese Patent Publication No. 6 proposes a structure of a water-absorbing pigment-containing layer and a pseudo-boehmite layer. In addition, JP-A-10-119424
Issue, Dohei 10-193776, Do 2000-1418
69, 2000-218927, 2000-3
55163, 2001-171228, 200
No. 1,171,224 and 2001-15806 disclose recording materials having a two-layer structure.

However, in the ink jet recording material having a plurality of constitutions composed of the solid fine particles as described above, a problem that a clear image immediately after printing, but an image bleeds under high humidity, newly occurred. In particular, when the indoor humidity is high, such as in the case of rain, bleeding may occur within a few hours after printing. Further, even in fine weather with relatively low humidity, similar image bleeding may occur in a few days.

It is considered that the above-mentioned bleeding phenomenon affects the rate of volatilization of the solvent in the ink of the upper layer and the lower layer when the ink is dried. For example, when the volatilization rate of the solvent in the lower layer is faster than that in the upper layer, the solvent becomes congested at the interface between the upper and lower layers, the amount of solvent locally increases, and one of the coloring agents fixed at some fixing site It is presumed that the image is blurred because the part starts to dissolve in the solvent again and moves.

On the other hand, as an ink jet recording material using a water repellent substance, there are disclosed in JP-A Nos. 7-96654 and 8-
No. 258397, No. 8-337050, No. 9-142
No. 008, No. 10-114141, No. 11-5893.
No. 4, 2000-158805 and the like, both describe the effect of the water-repellent substance near the surface of the recording sheet.

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a recording material having a multi-layer structure composed of solid fine particles, which is excellent in glossiness, ink absorption, printing density, and color developability, and which is used for image formation with time. It is to prevent bleeding.

[0012]

The above object of the present invention is to provide an ink jet recording material having at least two ink receiving layers mainly composed of solid fine particles on a support.
This was basically achieved by an ink jet recording material characterized in that the ink receiving layer A on the side closer to the support of the ink receiving layer contained a water repellent substance.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
As the support used in the present invention, a plastic resin film such as polyethylene, polypropylene, polyvinyl chloride, diacetate resin, triacetate resin, cellophane, acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polyethylene on one side or both sides of the paper substrate, etc. Water-resistant support such as resin-coated paper coated with polyolefin resin, fine paper, art paper, coated paper,
A water absorbing support such as cast coated paper is used. A water resistant support is preferably used. In particular, those having a thickness of about 50 to 300 μm are preferably used. For the recording material of the present invention, it is preferable to use a water-resistant support which is advantageous in terms of photographic-like gloss, texture, handleability and the like. However, unlike the paper support, since the water-resistant support does not absorb the solvent in the ink, bleeding easily occurs, which is the subject of the present invention, and therefore the effect of the present invention when using the water-resistant support is Remarkably expressed.

The ink jet recording material of the present invention is one in which at least two ink receiving layers mainly containing solid fine particles are laminated on the above support. Here, containing the solid fine particles as the main component means that the solid fine particles are 50% by weight or more, preferably 60% by weight based on the total solid content of the ink receiving layer.
It means that the content is at least wt. Particularly preferably,
That is, 65% by weight or more of solid fine particles are contained.

In the present invention, inorganic and organic fine particles are used as the solid fine particles, and the inorganic fine particles are preferable from the viewpoint of ink absorbability. As the inorganic fine particles, silica,
Inorganic fine particles known in the art such as alumina, hydrated alumina, and calcium carbonate are used. Of these, vapor phase silica and alumina or alumina hydrate are particularly preferably used. The average primary particle diameter of these inorganic fine particles is preferably about 3 to 50 nm.

In the recording material of the present invention, the water-repellent substance is contained in the ink receiving layer A, which is closer to the support, among the at least two ink receiving layers mainly containing solid fine particles. The water-repellent substance used in the present invention can be appropriately selected and used from known substances. For example, petroleum waxes such as paraffin wax and microcrystalline wax, natural waxes such as beeswax and carnauba wax, fatty acids such as stearic acid, myristic acid and oleic acid,
Metal soaps such as calcium stearate and zinc stearate, fatty acid chromium complex salts such as stearic acid chromic chloride complex salt and myristic acid chromic chloride complex salt,
Examples thereof include polyester resins such as alkyd resins and maleic acid resins, polyethylene emulsions, silicone resins, zirconium water repellents, polystyrene resins and polystyrene-acrylic acid ester copolymers, and cationic sizing agents such as rosin. You may use these water-repellent substances in combination of 2 or more types.

The water-repellent substance is preferably used in the range of 0.5 to 30% by weight based on the solid fine particles of the ink receiving layer A. The water-repellent substance is preferably not contained in the ink receiving layer B which is an upper layer of the ink receiving layer A (a layer distant from the support), but may be contained in an amount not deteriorating the color developability. For example, it may be contained in an amount of 0.5% by weight or less.

In the present invention, it is preferable that vapor phase silica is used for the ink receiving layer A and vapor phase silica, alumina, or alumina hydrate is used for the ink receiving layer B. Further, the average primary particle diameter of the solid fine particles used in the ink receiving layer A is preferably larger than that of the solid fine particles used in the ink receiving layer. With such an ink receiving layer configuration, various performances required for the inkjet recording material as described above can be obtained at a high level, but on the other hand, bleeding easily occurs over time after printing. Become. Therefore, the present invention has found that the above problems can be solved by incorporating the water-repellent substance in the lower ink receiving layer A.

The inorganic fine particles preferably used in the present invention will be described in detail below. The vapor phase silica is also called a dry method, and is generally produced by a flame hydrolysis method. Specifically, a method of burning silicon tetrachloride with hydrogen and oxygen is generally known, but instead of silicon tetrachloride, silanes such as methyltrichlorosilane and trichlorosilane may be used alone or in the form of silicon tetrachloride. It can be used as a mixture with. The vapor phase silica is available from Aerosil Japan and QS from Tokuyama Corporation.
It is commercially available as a type and can be obtained. The average primary particle diameter of the vapor phase method silica used in the present invention is 3
.About.50 nm is preferable, and a range of 3 to 30 nm is more preferable. The vapor-phase method silica aggregates into secondary particles having appropriate voids, and is pulverized with ultrasonic waves, a high-pressure homogenizer, an opposed collision type jet pulverizer, a ball mill, etc. until it becomes a secondary particle of about 50 to 300 nm. A dispersion is preferable because it has good ink absorbency and gloss.

Alumina and hydrated alumina are aluminum oxide and hydrates thereof, which may be crystalline or amorphous, and those having an amorphous shape, a spherical shape, a plate shape or the like are used. It Either of them may be used, or they may be used in combination.

As the alumina of the present invention, γ-alumina which is a γ-type crystal of aluminum oxide is preferable, and δ is particularly preferable.
Group crystals are preferred. γ-alumina has 1 primary particle
It is possible to reduce the particle size to about 0 nm, but usually, secondary particle crystals of thousands to tens of thousands nm are crushed to about 50 to 300 nm with an ultrasonic wave, a high pressure homogenizer, an opposed collision type jet crusher, a ball mill or the like. Those that can be preferably used.

The alumina hydrate of the present invention is Al ₂ O ₃ .nH
It is represented by a constitutive formula of 2O (n = 1 to 3). When n is 1, it represents an alumina hydrate having a boehmite structure, and when n is more than 1 and less than 3, it is an alumina hydrate having a pseudo-boehmite structure. It can be obtained by a known production method such as hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali, and hydrolysis of aluminate. The average particle diameter of primary particles of alumina and alumina hydrate used in the present invention is 10 to 50 n.
m is preferable, and more preferably 10 to 30 nm.

The average particle size of the primary particles of the fumed silica, alumina, and alumina hydrate of the present invention means that the dispersed particles are present within a certain area by observation with an electron microscope.
The diameter of a circle equal to the projected area of each individual particle can be obtained as the particle size of the particle. Further, the average particle size of secondary particles of vapor phase method silica, alumina, and alumina hydrate can be measured with a laser diffraction / scattering type particle size distribution analyzer for a diluted dispersion liquid.

[0024] In the present invention, preferably contains in the range of 8~30g / m ² of solid particles in the ink-receiving layer A, a range of 10~28g / m ² is more preferable. Preferably contains in the range of 0.5~18g / m ² of solid particles in the ink-receiving layer B, the range of 1~14g / m ² is more preferable. Furthermore, the total content of solid fine particles in the ink receiving layers A and B is preferably in the range of 12 to 35 g / m ² , and 15 to 15 g / m ^2.
A range of 32 g / m ² is more preferable.

In the present invention, a particularly preferred embodiment among the above-mentioned layer constitutions is to use vapor phase silica for the ink receiving layer A and use alumina or alumina hydrate for the ink receiving layer B. With this configuration, the ink having a good surface glossiness, the ink printed on the surface layer is promptly absorbed by the ink receiving layer A, and a printed image with good color development can be obtained.

The ink receiving layer of the present invention has a binder for maintaining the properties as a film. As this binder, various known binders can be used, but a hydrophilic binder having high transparency and high ink permeability can be preferably used. In using the hydrophilic binder, it is important that the hydrophilic binder does not swell and block the voids at the initial penetration of the ink. From this viewpoint, a hydrophilic binder having a low swelling property at around room temperature is preferable. Used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol.

Among the polyvinyl alcohols, those partially or completely saponified with a saponification degree of 80% or more are particularly preferable. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferable.

As the cation-modified polyvinyl alcohol, for example, as described in JP-A-61-10483, primary to tertiary amino groups and quaternary ammonium groups are added to the main chain or side chain of polyvinyl alcohol. It is a polyvinyl alcohol.

Further, other hydrophilic binders can be used in combination, but it is preferably 20% by weight or less with respect to polyvinyl alcohol.

In the present invention, in each layer of the ink receiving layer,
The weight ratio of the solid fine particles and the hydrophilic binder is preferably in the range of solid fine particles: hydrophilic binder = 60: 40 to 92: 8, more preferably 70:30 to 90:10.

The ink-receiving layer of each layer of the present invention preferably contains a cationic compound for the purpose of improving water resistance.
Examples of the cationic compound include cationic polymers and water-soluble metal compounds.

Examples of the cationic compound used in the present invention include cationic polymers and water-soluble metal compounds. Examples of the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, JP-A-59-20696, JP-A-59-33176, and JP-A-59-33176.
9-33177, 59-155088, 60-
11389, 60-49990 and 60-838.
No. 82, No. 60-109894, No. 62-19849.
No. 3, No. 63-49478, No. 63-115780.
No. 63-280681, JP-A-1-40371.
Polymers having a primary to tertiary amino group and a quaternary ammonium salt group described in JP-A Nos. 6-234268, 7-125411, 10-193776, etc. are preferably used. The molecular weight of these cationic polymers is
About 5,000 to 100,000 is preferable.

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

Examples of the water-soluble metal compound used in the present invention include water-soluble polyvalent metal salts. Examples thereof 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 chloride. Dicopper, ammonium chloride copper (II) dihydrate, copper sulfate, cobalt chloride,
Cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium ammonium hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum sulfite, Aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate,
Ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zirconium acetate, zirconium chloride, chloride Zirconium oxide octahydrate, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, sodium citrate tungsten, 12 tungstophosphate n Hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate and the like can be mentioned. Of these, zirconium compounds having high transparency and high water resistance improving effect are preferable.

Further, as the cationic compound, an inorganic type compound is used.
Basic polyhydric acid, an aluminum-containing cationic polymer
Aluminum compounds can be mentioned. Basic polyhydration
The aluminum compound has the following main formulas 1 and 2
Or 3 and, for example, [Al₆(OH)₁₅]³⁺, [A
l₈(OH)₂₀]⁴⁺, [Al₁₃(OH)₃₄]⁵⁺, [Al
_{twenty one}(OH)₆₀]³⁺Basic, macromolecular polynuclear contractions such as
Water-soluble polyaluminum hydroxide containing stable mixed ions
It is Ni.

[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 ... Equation 3

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

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

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

The ink receiving layer of each layer in the present invention preferably contains various oil droplets in order to improve the brittleness of the film. Such oil droplets have a solubility in water at room temperature of 0.01. A hydrophobic high-boiling point organic solvent (for example, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, etc.) or polymer particles (for example, styrene, butyl acrylate, etc.) in an amount of not more than wt% is used.
Particles obtained by polymerizing one or more polymerizable monomers such as divinylbenzene, butyl methacrylate, hydroxyethyl methacrylate) may be included. Such oil droplets are preferably 10 to 50 relative to the hydrophilic binder.
It can be used in the range of% by weight.

In the present invention, the ink receiving layer of each layer can be hardened with an appropriate hardener 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 chlorpentanedione, bis (2-chloroethylurea)-
2-Hydroxy-4,6-dichloro-1,3,5 triazine, compounds having reactive halogen such as those described in US Pat. No. 3,288,775, divinyl sulfone, described in US Pat. No. 3,635,718. A compound having a reactive olefin such as the above, an N-methylol compound as described in US Pat. No. 2,732,316, and US Pat.
Isocyanates such as those described in U.S. Pat. No. 3,437, aziridine compounds such as those described in U.S. Pat. Nos. 3,017,280 and 2,983,611, U.S. Pat.
No. 4, carbodiimide compounds, epoxy compounds as described in US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, boric acid and the like. There are inorganic hardeners such as borate, and these can be used alone or in combination of two or more. The amount of the hardener added is 0.0 with respect to 100 g of the water-soluble polymer constituting the ink receiving layer.
The amount is preferably 1 to 10 g, more preferably 0.1 to 5 g.

In the present invention, the ink receiving layer of each layer further comprises a coloring agent, a coloring pigment, a fixing agent for the ink dye, an ultraviolet absorber, an antioxidant, in addition to the surfactant and the hardener.
Various known additives such as a pigment dispersant, a defoaming agent, a leveling agent, a preservative, a fluorescent whitening agent, a viscosity stabilizer, and a pH adjusting agent may be added.

In the present invention, the ink receiving layer may be provided with a layer other than the ink receiving layers A and B, but in that case, it is necessary that the layer is a layer which does not impair ink permeability.

In the present invention, the coating method of each layer constituting the ink receiving layer can be a known coating method. For example, slide bead method, curtain method,
There are an extrusion method, an air knife method, a roll coating method, a ed bar coating method and the like.

In the present invention, the properties required for each layer are efficiently obtained by coating the respective layers constituting the ink receiving layers A and B such as the slide bead system almost simultaneously without providing a drying step. It is obtained well and is preferable in terms of production efficiency. That is, it is expected that by laminating each layer in a wet state, the components contained in each layer are less likely to penetrate into the lower layer, so that the component constitution of each layer is well maintained even after drying.

When the coating liquid for the ink receiving layer is applied to the film support or the resin-coated paper, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, plasma treatment or the like is preferably carried out prior to coating.

In the present invention, when a support, particularly a film or resin-coated paper which is a water-resistant support, is used, a primer layer mainly containing a natural polymer compound or a synthetic resin is provided on the surface on which the ink receiving layer is provided. Is preferably provided. The transparency of the ink receiving layer is further improved by coating the ink receiving layer containing the inorganic fine particles of the present invention on the primer layer, then cooling and drying at a relatively low temperature.

The primer layer provided on the support is mainly composed of natural polymer compounds such as gelatin and casein and synthetic resins. Examples of the synthetic resin include acrylic resin, polyester resin, vinylidene chloride, vinyl chloride resin, vinyl acetate resin, polystyrene, polyamide resin, and polyurethane resin.

The above-mentioned primer layer is formed on the support by 0.01
It is provided with a film thickness (dry film thickness) of ˜5 μm. It is preferably in the range of 0.05 to 5 μm.

Various back coat layers can be coated on the support of the present invention for the purposes of writing, antistatic properties, transportability and curl prevention. The back coat layer may contain an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a pigment, a curing agent, a surfactant and the like in an appropriate combination.

[0051]

EXAMPLES Example 1 Hereinafter, the present invention will be described in detail with reference to Examples, but the content of the present invention is not limited to the Examples. Incidentally, part and%
Indicates parts by weight and% by weight.

<Preparation of Polyolefin Resin Coated Paper Support> A 1: 1 mixture of a bleached hardwood kraft pulp (LBKP) and a bleached softwood sulfite pulp (NBSP) was beaten to 300 ml with Canadian Standard Freeness to prepare a pulp slurry. did. Alkyl ketene dimer as a sizing agent was added to the pulp in an amount of 0.5% by weight, and polyacrylamide as a strength agent was added to the pulp in an amount of 1.0.
% By weight, cationized starch to pulp 2.0% by weight, polyamide epichlorohydrin resin to pulp 0.5% by weight
Add and dilute with water to give a 1% slurry. This slurry was made into a paper by a Fourdrinier paper machine so as to have a basis weight of 170 g / m ² , dried and conditioned to obtain a base paper for a polyolefin resin-coated paper. A polyethylene resin composition in which 10% by weight of anatase-type titanium was uniformly dispersed in 100% by weight of a low density polyethylene resin having a density of 0.918 g / cm ³ was melted at 320 ° C. in a paper-making base paper, and 200 m / Thickness in minutes 3
It was extrusion-coated so as to have a thickness of 5 μm, and was extrusion-coated using a cooling roll having a finely roughened surface. Similarly, on the other surface, a blended resin composition of 70 parts by weight of a high density polyethylene resin having a density of 0.962 g / cm ³ and 30 parts by weight of a low density polyethylene resin having a density of 0.918 was added in the same amount as 320 parts.
It was melted at 0 ° C., extrusion coated to a thickness of 30 μm, and extrusion coated using a roughened cooling roll.

After the high frequency corona discharge treatment was applied to the surface of the above polyolefin resin-coated paper, a primer layer having the following composition was coated and dried so that gelatin was 50 mg / m ² to prepare a support.

[0054] <Primer layer> 100 parts of lime-processed gelatin Sulfosuccinic acid-2-ethylhexyl ester salt 2 parts Chrome Alum 10 copies

Coating solutions for the respective ink receiving layers having the following compositions were simultaneously coated on the above-mentioned support with a slide bead coating apparatus and dried. The additives shown in Table 1 were further added to the ink receiving layer coating liquid A before coating. The coating amount of the ink-receiving layer A was applied to 18 g / m ^2, the ink receiving layer B1 is 6 g / m ^2.

[0056] <Ink receiving layer coating liquid A> 100 parts of vapor phase silica   (Average primary particle size 20 nm) Dimethyldiallylammonium chloride homopolymer 4 parts Boric acid 3 parts Polyvinyl alcohol 20 parts   (Saponification degree 88%, average degree of polymerization 3500) Surfactant (betaine) 0.2 parts Zirconium hydroxychloride 2 parts Poly aluminum hydroxide 4 parts

[0057] <Ink receiving layer coating liquid B1> 100 copies of pseudo-boehmite   (Average primary particle size 14 nm, aspect ratio 2) Boric acid 0.4 parts Polyvinyl alcohol 10 parts   (Saponification degree 88%, average degree of polymerization 3500) Surfactant (betaine) 0.2 parts

[0058]

[Table 1] For samples 6 and 7, a commercially available cationic styrene-acrylic acid ester resin was used as a cationic sizing agent.

The following evaluations were performed on the ink jet recording sheet prepared as described above. The results are shown in Table 2.

<Ink Absorption> A commercially available inkjet printer (PM880C manufactured by Seiko Epson Corporation) was used to print solid colors of four colors of red, blue, green and black from 0 to 0.
Gradation was applied at 100% output, and one minute after the completion of printing, PPC paper was overlaid on the printing portion and lightly pressure-bonded, and the extent of the amount of ink transferred to the PPC paper was visually observed. The overall evaluation was made based on the following criteria. ◯: No transfer is performed. Δ: Transfer a little. X: Transfer is large and cannot be actually used.

<Printing Density> The printing density of a solid black portion was measured with a Macbeth reflection densitometer and shown as an average value of 5 measurements.

<Color Development> The optical densities of the solid portions of C, M, Y and K were measured by a Macbeth reflection densitometer and the total optical densities of the respective colors were shown. The larger the number, the better the color development. <Glossiness of blank part> The glossiness of the blank part of the recording material before printing was observed by oblique light and evaluated according to the following criteria. ⊚: Extremely high glossiness similar to color photographs ○: High glossiness ×: Sunk glossiness

<Bleeding under high humidity> A sample dried at least 12 hours after image printing was dried at 40 ° C. and 85% R.V. H. The condition of bleeding was visually evaluated for the ones which had been seasoned for 24 hours under the conditions. ◎: No bleeding ○: Slight bleeding is observed △: Bleeding is recognized ×: Remarkably bleeding

[0064]

[Table 2]

Example 2 A sample was prepared and evaluated in the same manner as in Example 1 except that the ink receiving layer coating liquid B2 shown below was used in place of the ink receiving layer coating liquid B1.

[0066] <Ink receiving layer coating liquid B2> 100 parts of vapor phase silica   (Average primary particle size 7 nm) Dimethyldiallylammonium chloride homopolymer 4 parts Boric acid 3 parts Polyvinyl alcohol 20 parts   (Saponification degree 88%, average degree of polymerization 3500) Surfactant (betaine) 0.2 parts Zirconium hydroxychloride 2 parts Poly aluminum hydroxide 4 parts Additive (same as Table 1)

[0067]

[Table 3]

From the results of Tables 2 and 3, the recording sheet containing the water-repellent substance suppresses bleeding under high humidity, and the slight decrease in print density and gloss caused by the water-repellent substance is further caused. It is apparent that the improvement is provided by providing the ink absorbing layer.

[0069]

As is clear from the above results, the ink jet recording material of the present invention has high gloss, is excellent in ink absorbency, print density and color development, and is excellent in suppressing the occurrence of image bleeding over time. The material is obtained.

Claims (4)

[Claims] 1. In an ink jet recording material having at least two layers of an ink receiving layer mainly composed of solid fine particles on a support, the ink receiving layer A on the side closer to the support in the ink receiving layer is a water repellent substance. An ink jet recording material comprising: 2. The solid fine particles of the ink receiving layer A are vapor phase silica, and the solid fine particles of the ink receiving layer B provided on the side farther from the support than the ink receiving layer A are vapor phase silica, alumina, Alternatively, the inkjet recording material according to claim 1, which is an alumina hydrate. 3. The inkjet recording material according to claim 1, wherein the primary average particle diameter of the solid fine particles of the ink receiving layer A is larger than the primary average particle diameter of the solid fine particles of the ink receiving layer B. 4. The ink jet recording material according to claim 1, 2 or 3, wherein the support is a water resistant support.