JP2001260519A - Ink jet recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording material for revising photo-like high gloss, high ink absorbability and storage stability. SOLUTION: The ink jet recording material comprises an ink acceptive layer containing inorganic fine particles on a support. In this case, the ink acceptive layer contains a sulfine compound, a thiosulfine compound or a thiosulfone compound. Further, the layer also contains at least one compound selected from thiourea compounds, saccharides, pyridine compounds, thioether compounds disulfide compounds and thiazine compounds.

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 more particularly to an ink-jet recording material having high photo-like gloss, excellent ink absorbency, and improved storage stability after printing. It is.

[0002]

2. Description of the Related Art As a recording material used in an ink jet recording system, a pigment such as amorphous silica is coated on a support called a normal paper or an ink jet recording paper by a porous material comprising a water-soluble binder such as polyvinyl alcohol. There is known a recording material provided with an ink absorbing layer.

[0003] For example, Japanese Patent Application Laid-Open No. 55-51583,
Nos. 6-157, 57-107879, 57-10
No. 7880, No. 59-230787, No. 62-160
No. 277, No. 62-184879, No. 62-1833
As disclosed in JP-A-82 and JP-A-64-11877, a recording material obtained by applying a silicon-containing pigment such as silica to a paper support together with an aqueous binder has been proposed.

[0004] Also, Japanese Patent Publication No. 3-56552,
No. 188287, No. 10-81064, No. 10
-119423, 10-175365, 1
Nos. 0-193776, 10-203006, 10
-217601, 11-20300, 11
Japanese Patent Publication Nos. -20306 and 11-34481 disclose the use of vapor-phase synthetic silica fine particles (hereinafter referred to as fumed silica). This fumed silica is an ultrafine particle having an average primary particle diameter of several nm to several tens nm, and is characterized in that high gloss is obtained.
In recent years, with the demand for photo-like recording sheets, glossiness has been increasingly emphasized, and water resistance of polyolefin resin-coated paper (a laminate of a polyolefin resin such as polyethylene on both sides of paper) and polyester film There has been proposed a recording material in which an ink receiving layer mainly composed of fumed silica is provided on a support.

Conventionally, a paper support generally used itself has a role as an ink absorbing layer. However, a water-resistant support such as the above-mentioned polyolefin resin-coated paper is a paper support. Unlike the above, ink cannot be absorbed, so that the ink absorbing property of the ink receiving layer provided on the support is important, and it is necessary to increase the porosity of the ink receiving layer. Therefore, it was necessary to increase the coating amount of the fumed silica and further reduce the ratio of the binder to the fumed silica.

However, a porous recording material using inorganic fine particles such as fumed silica has a problem that a printed image is liable to be discolored during storage after printing. That is, discoloration due to light and discoloration due to a trace amount of gas in the air were likely to occur. In particular, discoloration due to trace gases in the atmosphere was a more important problem.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ink-jet recording material having improved photo-like high gloss, high ink absorption and storage stability.

[0008]

An object of the present invention is to provide an ink jet recording material having an ink receiving layer containing inorganic fine particles on a support, wherein the ink receiving layer comprises a sulfinic acid compound, a thiosulfonic acid compound, and a thiosulfonic acid compound. This has been attained by an ink jet recording material characterized by containing at least one sulfinic acid compound. Preferably, the inkjet recording material further comprises at least one compound selected from a thiourea compound, a saccharide, a pyridine compound, a thioether compound, a disulfide compound, and a thiazine compound.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the ink jet recording material of the present invention, the ink is absorbed in the voids formed in the film by the silica fine particles, and it is necessary to increase the void volume in order to exhibit high ink absorbency. For this reason, it is necessary to apply a relatively large amount of silica fine particles on the support, and it is preferable to reduce the amount of the hydrophilic binder in order to increase the porosity.

The inorganic fine particles used in the present invention include:
Known various fine particles such as silica and alumina,
Vaporized silica is most preferred. The ink receiving layer preferably contains 8 g / m ² or more of fumed silica.
More preferably, it is used in the range of 30 g / m ² . If the amount is less than this range, the ink absorbency is poor. The amount of the hydrophilic binder is preferably 40% by weight or less, more preferably 10 to 30% by weight, based on the fumed silica. By reducing the ratio of the hydrophilic binder as described above, the ink absorbency is improved, but the storage stability after printing, particularly the gas resistance, tends to decrease, and the present invention is intended to simultaneously satisfy these performances. Features.

In the present invention, the fumed silica accounts for 50% by weight or more, preferably 6% by weight, based on the total solid content of the ink receiving layer.
The content is preferably 0% by weight or more, more preferably 65% by weight or more.

Synthetic silica includes those obtained by a wet method and those obtained by a gas phase method. As wet silica, silica sol obtained by metathesis of sodium silicate with an acid or the like through an ion exchange resin layer, or colloidal silica obtained by heating and aging this silica sol, gelling silica sol, and changing the production conditions Silicic acid such as silica gel in which primary particles of several microns to 10 microns have become siloxane-bonded three-dimensional secondary particles, and those obtained by heating and producing silica sol, sodium silicate, sodium aluminate, etc. And the like.

The fumed silica is also called a dry method as opposed to a wet method, and is generally produced by a flame hydrolysis method. Specifically, a method of making silicon tetrachloride by burning it with hydrogen and oxygen is generally known, but instead of silicon tetrachloride, silanes such as methyltrichlorosilane and trichlorosilane may be used alone or in a silicon tetrachloride. And can be used in a mixed state. The fumed silica is Aerosil from Nippon Aerosil Co., Ltd. and Q from Tokuyama Co., Ltd.
It is commercially available as the S type and can be obtained.

The average particle size of the primary particles of the fumed silica particularly preferably used in the present invention is preferably 30 nm or less, and in order to obtain higher gloss, it is preferably 15 nm or less. More preferably, the average particle size of the primary particles is 3 to 15 n.
m (in particular 3 to 10 nm) a and a specific surface area by BET method is 200 meters ² / g or more (preferably 250~500m ² /
g). The BET method referred to in the present invention is one of the methods for measuring the surface area of a powder by a gas phase adsorption method, and is a method for determining the total surface area of 1 g of a sample, that is, the specific surface area, from an adsorption isotherm. Usually, nitrogen gas is often used as the adsorbed gas, and the method of measuring the amount of adsorption from the change in pressure or volume of the gas to be adsorbed is most often used. The most prominent to represent the isotherm for multimolecular adsorption is
This is a formula of Brunauer, Emmett, Teller, called a BET formula, which is widely used for determining the surface area. The surface area is obtained by calculating the amount of adsorption based on the BET formula and multiplying the area occupied by one adsorbed molecule on the surface.

In the present invention, as the hydrophilic binder used together with the fumed silica, various known binders can be used, but a hydrophilic binder which has high transparency and can obtain higher ink permeability is preferably used. Can be In the use of the hydrophilic binder, it is important that the hydrophilic binder does not swell at the initial penetration of the ink and does not close the voids.From this viewpoint, a hydrophilic binder having a relatively low swelling property at around room temperature is preferable. Used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohols or cationically modified polyvinyl alcohols.

Particularly preferred among polyvinyl alcohols are those partially or completely saponified with a saponification degree of 80 or more. Those having an average polymerization degree of 200 to 5000 are preferred.

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

In the present invention, it is preferable to use a crosslinking agent (hardening agent) together with the hydrophilic binder. Specific examples of the crosslinking agent 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 U.S. Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in U.S. Pat. No. 3,635,718, U.S. Pat. 2nd, 73
N-methylol compounds as described in U.S. Pat. No. 2,316, isocyanates as described in U.S. Pat. No. 3,103,437, U.S. Pat. Nos. 3,017,280 and 2,983,
611, carbodiimide compounds as described in U.S. Pat. No. 3,100,704, epoxy compounds as described in U.S. Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid, There are dioxane derivatives such as dihydroxydioxane, and inorganic crosslinking agents such as chromium alum, zirconium sulfate, boric acid and borate, and these can be used alone or in combination of two or more. Among these, boric acid or borate is particularly preferred.

[0019] The present invention relates to a method for producing a fumed silica,
By using a sulfinic acid compound, a thiosulfonic acid compound, or a thiosulfinic acid compound, the storage stability after printing is remarkably improved.

As the sulfinic acid compound, a compound represented by the following general formula (4) is preferable.

[0021]

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In the general formula (4), R is a substituted or unsubstituted alkyl group (preferably having 6 to 30 carbon atoms) or a substituted or unsubstituted aryl group (a phenyl group, a naphthyl group or the like, and preferably has 6 carbon atoms). To 30). M represents a hydrogen atom, an alkali metal atom, or ammonium.

The substituent of the group represented by R includes:
A linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably monocyclic or bicyclic, having 1 to 3 carbon atoms in the alkyl portion), an alkoxy group (preferably having 1 carbon atom) 20) a mono- or di-substituted amino group (preferably an alkyl group having 1 to 20 carbon atoms, an acyl group, an alkyl or aryl sulfonyl group,
In the case of substitution, the total number of carbon atoms in the substituent is 20 or less, a substituted or unsubstituted ureido group (preferably having 1 to 20 carbon atoms), a substituted or unsubstituted aryl group (preferably Is a monocyclic or bicyclic one having 6 to 29 carbon atoms), a substituted or unsubstituted arylthio group (preferably having 6 to 29 carbon atoms), a substituted or unsubstituted alkylthio group (preferably having 1 to 29 carbon atoms), Substituted or unsubstituted alkylsulfoxy group (preferably having 1 to 29 carbon atoms), substituted or unsubstituted arylsulfoxy group (preferably having 6 to 29 carbon atoms and monocyclic or bicyclic), substituted or unsubstituted Alkylsulfonyl group (preferably having 1 to carbon atoms)
29), a substituted or unsubstituted arylsulfonyl group (preferably monocyclic or bicyclic having 6 to 29 carbon atoms),
An aryloxy group (preferably having 6 to 29 carbon atoms and a monocyclic or bicyclic ring), a carbamoyl group (preferably having 1 to 29 carbon atoms), a sulfamoyl group (preferably having 1 carbon atom)
To 29), a hydroxy group, a halogen atom (fluorine, chlorine, bromine, iodine), a sulfonic acid group, or a carboxylic acid group.

These substituents further include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group and a sulfamoyl group. , An alkylsulfoxy group, an arylsulfoxy group, an ester group, a hydroxy group, a carboxy group, a sulfo group, a substituent such as a halogen atom. These groups may be connected to each other to form a ring. Also, these groups may be part of a homopolymer or copolymer chain.

As the thiosulfonic acid compound, a compound represented by the following general formula (5) is preferable.

[0026]

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In the general formula (5), Z represents a substituted or unsubstituted alkyl group (preferably having 1 to 18 carbon atoms), a substituted or unsubstituted aryl group (preferably having 6 to 18 carbon atoms) or a substituted or unsubstituted heterocyclic group. Y represents an atom necessary for forming a substituted or unsubstituted aromatic ring (preferably having 6 to 18 carbon atoms) or a substituted or unsubstituted heterocyclic ring. M represents a metal atom or an organic cation, and n represents an integer of 2 to 10.

Examples of the substituents of the groups represented by Z and Y include lower alkyl groups such as methyl group and ethyl group, aryl groups such as phenyl group, alkoxy groups having 1 to 8 carbon atoms, and chlorine. Halogen atom, nitro group, amino group,
A carboxy group and the like can be mentioned. The metal atom represented by M is preferably an alkali metal atom such as sodium or potassium, and the organic cation is preferably an ammonium or guanidine group.

As the thiosulfinic acid compound, a compound represented by the following general formula (6) is preferable.

[0030]

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Z, Y, M and n in the general formula (6) are the same as those in the general formula (5).

Specific examples of the above-mentioned sulfinic acid compound, thiosulfonic acid compound and thiosulfinic acid compound are shown below, but are not limited thereto.

[0033]

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[0034]

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[0035]

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[0036] The sulfinic acid compounds, thiosulfonic acid compounds, and the content in the ink receiving layer of the thiosulfinic acid compounds, 0.1 to 50 mmol / m ² preferably 0.2 to 20 mmol / m ² Gayori preferable.

In the present invention, in addition to at least one of (A) a sulfinic acid compound, a thiosulfonic acid compound and a thiosulfinic acid compound, the ink receiving layer further comprises (B) a thiourea compound, (C) a saccharide, and (D) a pyridine compound. Compound,
It is preferable from the viewpoint of image storability that at least one compound selected from the group consisting of (E) a thioether compound, (F) a disulfide compound, and (G) a thiazine compound is contained. When used in combination, the image storability is significantly improved as compared with the use of compound (A) alone. Compound (B)-
Since the mechanism of improving the image storability by (G) is different from that of compound (A), it is expected that a synergistic effect will be obtained by complementing each other.

The thiourea compound of the compound (B) of the present invention is preferably a compound having at least one structure of the above general formula (1) in the molecule, and is preferably thiourea, N-methylthiourea, N-acetylthiourea. 1,3-diphenylthiourea, tetramethylthiourea, guanylthiourea, 4-methylthiosemicarbazide, 1,3
-Bis (hydroxymethyl) -2 (3H) benzimidazolethione, 6-hydroxy-1-phenyl-3,4
-Dihydropyrimidine-2 (1H) -thione, 1-allyl-2-thiourea, 1,3-dimethyl-2-thiourea, 1,3-diethyl-2-thiourea, ethylenethiourea, trimethylthiourea, 1-carboxymethyl- 2-thiohydantoin, thiosemicarbazide and the like can be mentioned.

The saccharides of the compound (C) of the present invention include, for example, D-glucose, D-ribose, maltose, cellobiose, melibiose, gentiobiose, D-glucosamine, D-xylose, D-galactose, lactose, vicianose, turanose. , Gentianose,
Monosaccharides and oligosaccharides such as rutinose, L-xylose, L-sorbose, D-mannitol, trehalose, D-fructose, sucrose, raffinose, and stachyose. Oligosaccharides are also called oligosaccharides and refer to saccharides having a degree of polymerization from disaccharide to pentasaccharide. More preferably, a reducing sugar having a reducing group such as D-glucose, lactose, D-ribose, maltose, trehalose or the like is selected from the effect of improving light fastness.

The pyridine compound of the compound (D) of the present invention includes 4-aminomethylpyridine, 4-chloropyridine hydrochloride, 4-hydroxypyridine, 4-cyanopyridine, 3-cyanopyridine, 2,2'- Bipyridine, isonicotinamide, methyl isonicotinate, 3-hydroxypyridine, 3,4-dihydroxypyridine, 3-
Piperidinopyridine, 3-aminomethylpyridine, 2,
4-dicyanopyridine, 2,4-dihydroxypyridine, 2- (2-hydroxyethyl) pyridine and the like. Preferred are 4-aminomethylpyridine, 4-chloropyridine hydrochloride, 4-hydroxypyridine, 4-cyanopyridine, 3-cyanopyridine, 2,2′-bipyridine, isonicotinamide and methyl isonicotinate.

The thioether compound of the compound (E) is preferably a compound represented by the above general formula (2), and in particular, 3,6-dithio-1,8-octanediol and bis [2- (2 -Hydroxyethylthio) ethyl]
Sulfone, 3,6,9-trithio-1,11-undecanediol, 4- (methylthio) phenol, 2- (phenylthio) ethanol are preferred.

The disulfide compound of the compound (F) is preferably a compound represented by the aforementioned general formula (3), particularly DL-α-lipoic acid, 4,4′-dithiodimorpholine, 4'-dithiodibutanoic acid is preferred.

The thiazine compound of the compound (G) is preferably a mercaptothiazine compound, especially 5,6-dihydro- (4H) -1,3-thiazine-2.
-Thiol, 3-benzyl-1,3-thiazinan-2-
Thione, 3-methyl-1,3-thiazinane-2-thione, 5,6-dihydro-2-methylthio-4H-1,3
-Thiazine, 3-carboxymethyl-6,6-dimethyl-4-oxo-1,3-thiazinane-2-thione is preferred.

The compounds of the present invention (B) ~ content in the ink receiving layer of the compound of (G) is preferably 0.1 to 50 mmol / m ² and more preferably 0.2 to 20 mmol / m ² .

The ratio of the content of each of the compounds (A) to (G) of the present invention in the ink receiving layer is not particularly limited, but the maximum amount of the compound is approximately within 100 times the minimum amount of the compound,
Preferably it is within 10 times.

In the present invention, the ink receiving layer may be applied in two or more layers, or after the ink receiving layer containing no compounds (A) to (G) is provided, the compounds (A) to (G) may be applied. ) May be applied or impregnated, or may be contained in the uppermost layer of the ink receiving layer. In particular, in the case of a compound that increases the viscosity of one coating liquid of the ink receiving layer, it is preferable to separately apply the coating liquid.

In the present invention, at least one compound (A)
One or more compounds selected from the species and the compounds (B) to (G) may be separately contained in separate layers constituting the recording material for inkjet, and each compound may be used as a recording material. It is more preferable to be in contact with the printed ink colorant from the viewpoint of light resistance, and it is preferable to increase the content of each compound in the upper layer away from the support from the viewpoint of gas resistance.

The ink receiving layer of the present invention preferably contains a cationic compound. By using the above compound and a cationic compound in combination, the storage stability is further improved.

Examples of the cationic compound include a cationic polymer and a water-soluble metal compound. Examples of the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, and alkylamine polymers, JP-A-59-20696 and JP-A-59-33176.
No. 59-33177, No. 59-155088,
No. 60-11389, No. 60-49990, No. 60
No. 83882, No. 60-109894, No. 62-1
Nos. 98493, 63-49478, 63-115
780, 63-280681, JP-A-1-403
No. 71, No. 6-234268, No. 7-125411
Nos. 1 to 3 described in JP-A-10-193776 and the like.
A polymer having a quaternary amino group and a quaternary ammonium group is preferably used. The molecular weight of these cationic polymers is preferably 5,000 or more, and more preferably 5,000 to 1
About 100,000 is preferable.

These cationic polymers are used in an amount of 1 to 10% by weight, preferably 2 to 7% by weight, based on fumed silica.
% By weight.

The water-soluble metal compound used in the present invention includes, for example, water-soluble polyvalent metal salts. 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, chlorinated chloride Cupric, ammonium copper (II) chloride dihydrate, copper sulfate, cobalt chloride,
Cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium sulfate hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum sulfite, Aluminum thiosulfate, poly aluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate,
Ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc phenolsulfonate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zirconium acetate , Zirconium chloride, zirconium chloride octahydrate, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate,
Magnesium citrate nonahydrate, sodium phosphotungstate, sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphate n hydrate and the like Can be

In the present invention, a water-soluble aluminum compound or a water-soluble compound containing a Group 4A element in the periodic table is particularly preferable. As the water-soluble aluminum compound, for example, as an inorganic salt, aluminum chloride or a hydrate thereof, aluminum sulfate or a hydrate thereof, ammonium alum and the like are known. Further, there is a basic polyaluminum hydroxide compound which is an inorganic aluminum-containing cationic polymer. Particularly, a basic polyaluminum hydroxide compound is preferable.

The basic polyaluminum hydroxide compound has a main component represented by the following general formula 1, 2 or 3, for example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ⁴⁺ ,
It is a water-soluble polyaluminum hydroxide stably containing basic and high-molecular polynuclear condensed ions such as [Al ₁₃ (OH) ₃₄ ] ⁵⁺ , [Al ₂₁ (OH) ₆₀ ] ³⁺ , and the like. .

[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 under the name of polyaluminum chloride (PAC) from Taki Chemical Co., Ltd., and 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 readily available. In the present invention, these commercial products can be used as they are,
Some substances have an inappropriately low pH, and in such a case, the pH can be appropriately adjusted and used.

The water-soluble compound containing a Group 4A element in the periodic table used in the present invention is not particularly limited as long as it is water-soluble, but a water-soluble compound containing titanium or zirconium is preferable.
For example, as a water-soluble compound containing titanium, titanium chloride,
Titanium sulfate is a water-soluble compound containing zirconium as zirconium acetate, zirconium chloride, zirconium oxychloride, zirconium hydroxychloride, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, zirconium ammonium carbonate, zirconium potassium carbonate, zirconium sulfate And zirconium fluoride compounds are known. Some of these compounds have an inappropriately low pH. In such a case, the pH can be appropriately adjusted and used. In the present invention, the term "water-soluble" refers to a condition in which 1% by weight or more is dissolved in water at normal temperature and normal pressure.

In the present invention, the content of the water-soluble metal compound in the ink receiving layer is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the fumed silica.
% By weight.

Two or more of the above-mentioned cationic compounds can be used in combination. For example, it is preferable to use a cationic polymer and a water-soluble metal compound in combination.

In the present invention, the pH of the surface of the ink receiving layer containing fumed silica is preferably 2 to 6, particularly preferably 3 to 5. By combining the above-mentioned compound of the present invention with this film surface pH, the storage stability is further improved. The pH of the surface of the ink receiving layer is determined by the method described in J. Org. TAPPI
This is the surface pH measured after 30 seconds using distilled water according to the method described in Paper Pulp Test Method N0.49.

The pH of the ink receiving layer is preferably adjusted at the stage of the coating solution. However, since the pH of the coating solution does not always match the pH of the film surface after the coating and drying, the coating solution and the film surface may be adjusted. It is necessary to determine the relationship with pH in advance by experiments or the like in order to obtain a predetermined film surface pH. The pH of the ink receiving layer coating solution is adjusted by appropriately combining an acid or an alkali. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid, citric acid, and succinic acid. Examples of the alkali include sodium hydroxide, ammonia water, potassium carbonate, and trisodium phosphate. Alternatively, as the weak alkali, an alkali metal salt of a weak acid such as sodium acetate is used.

The ink receiving layer of the present invention may contain various oil droplets for further improving the brittleness of the film.
Such oil droplets include hydrophobic high-boiling organic solvents having a solubility in water at room temperature of 0.01% by weight or less (for example, liquid paraffin, dioctyl phthalate, tricresyl phosphate, silicone oil, etc.) and polymer particles ( For example, particles obtained by polymerizing one or more polymerizable monomers such as styrene, butyl acrylate, divinylbenzene, butyl methacrylate, and hydroxyethyl methacrylate) can be contained. Such oil droplets can be preferably used in the range of 10 to 50% by weight based on the hydrophilic binder.

In the present invention, a surfactant can be added to the ink receiving layer. The surfactant used may be any of anionic, cationic, nonionic and betaine types, and may be of low molecular weight or high molecular weight. One or two or more surfactants are added to the ink receiving layer coating solution. When two or more surfactants are used in combination, an anionic surfactant and a cationic surfactant are used in combination. It is not preferable. The addition amount of the surfactant is preferably 0.001 to 5 g with respect to 100 g of the binder constituting the ink receiving layer,
More preferably, it is 0.01 to 3 g.

In the present invention, the ink receiving layer further comprises:
Publicly known coloring dyes, coloring pigments, fixing agents for ink dyes, ultraviolet absorbers, antioxidants, pigment dispersants, defoamers, leveling agents, preservatives, fluorescent brighteners, viscosity stabilizers, pH regulators, etc. Can be added.

The support used in the present invention is preferably a water-resistant support. As the water-resistant support, a polyester resin such as polyethylene terephthalate, a diacetate resin, a triacetate resin, an acrylic resin, a polycarbonate resin, a polyvinyl chloride, a polyimide resin, a plastic resin film such as cellophane and celluloid, and a polyolefin resin on both sides of paper And resin-coated paper laminated with The thickness of the water-resistant support used in the present invention is preferably about 50 to 300 μm.

The base paper constituting the resin-coated paper preferably used in the present invention is not particularly limited, and generally used paper can be used. More preferably, for example, a smooth paper such as that used for a photographic support is used. Base paper is preferred. As the pulp constituting the base paper, natural pulp, recycled pulp, synthetic pulp or the like may be used alone or in combination of two or more. This base paper contains sizing agents, paper strength agents, fillers, antistatic agents, fluorescent whitening agents,
Additives such as dyes are blended.

Further, a surface sizing agent, a surface paper strengthening agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchoring agent and the like may be coated on the surface.

The thickness of the base paper is not particularly limited, but preferably has good surface smoothness such as by applying a pressure by a calender or the like during or after the paper is made, and has a basis weight of 30%. ~250g / m ² is preferred.

As the resin of the resin-coated paper, a polyolefin resin or a resin that can be cured by an electron beam can be used.
The polyolefin resin is a low-density polyethylene, high-density polyethylene, polypropylene, polybutene, a homopolymer of an olefin such as polypentene or a copolymer of two or more olefins such as an ethylene-propylene copolymer and a mixture thereof, Those having various densities and melt viscosity indices (melt index) can be used alone or in combination.

In the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearamide, arachidic amide, zinc stearate, calcium stearate, stearic acid Aluminum, fatty acid metal salts such as magnesium stearate, antioxidants such as Irganox 1010 and Irganox 1076, blue pigments and dyes such as cobalt blue, ultramarine blue, cecilian blue, and phthalocyanine blue, cobalt violet, fast violet, and manganese purple It is preferable to add various additives such as magenta pigments and dyes, fluorescent brighteners and ultraviolet absorbers in an appropriate combination.

The resin-coated paper as a support preferably used in the present invention is produced by a so-called extrusion coating method in which, in the case of a polyolefin resin, a heat-melted resin is cast on a running base paper, the both surfaces of which are made of resin. Coated. In the case of a resin that is cured by an electron beam, the resin is applied by a commonly used coater such as a gravure coater or a blade coater, and then irradiated with an electron beam to cure and coat the resin. Further, before coating the resin on the base paper, the base paper is preferably subjected to an activation treatment such as a corona discharge treatment or a flame treatment. The surface (surface) of the support on which the ink receiving layer is applied has a glossy surface, a matte surface, and the like, depending on the application, and the glossy surface is used particularly advantageously. It is not necessary to coat the back surface with a resin, but it is preferable to coat the resin from the viewpoint of curling prevention. The back surface is usually a matte surface, and the front surface or both front and back surfaces can be subjected to an activation treatment such as a corona discharge treatment or a flame treatment as required. The thickness of the resin coating layer is not particularly limited, but is generally 5 to 50 μm thick on the surface or on both sides.

The support in the present invention may be coated with various back coat layers for antistatic properties, transport properties, curling prevention properties, and the like. The back coat layer can contain an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like in an appropriate combination.

In the present invention, the method for applying the ink receiving layer is not particularly limited, and a known coating method can be used. For example, there are a slide lip system, a curtain system, an extrusion system, an air knife system, a roll coating system, a rod bar coating system, and the like.

In the present invention, in addition to the layer containing fumed silica (this layer may be a plurality of layers), the ink-jet recording material further includes an ink absorbing layer, an ink fixing layer, an intermediate layer, and a protective layer. May be provided. For example, a water-soluble polymer layer may be provided as a lower layer, or a swelling layer may be provided as an upper layer.

[0074]

EXAMPLES The present invention will be described below in detail with reference to examples, but the contents of the present invention are not limited to the examples. In addition, a part means a solid content weight part.

Example 1 As a support, LBKP (50 parts) and LBSP (50 parts) were used.
Part) of a pulp blend of 120 g / m ^{2 and} a resin composition comprising low-density polyethylene (70 parts), high-density polyethylene (20 parts) and titanium oxide (10 parts) applied to the surface of 25 g / m ^2. And high-density polyethylene (50
Parts) and a low-density polyethylene (50 parts) resin coating paper prepared by applying 25 g / m ² .

An ink receiving layer coating solution having the following composition was prepared on the above support, and the coating amount of fumed silica was 18 g in solid content.
/ M ² and dried to prepare an ink jet recording sheet. In addition, all the recording sheets were adjusted so that the film surface pH of the ink receiving layer became 4.2.

<Recording sheet 1> 100 parts of fumed silica (average primary particle size: 7 nm, specific surface area by BET method: 300 m ² / g) 23 parts of polyvinyl alcohol (trade name: PVA235, manufactured by Kuraray Co., Ltd., degree of saponification) 88%, average polymerization degree 3500) Boric acid 4 parts Amphoteric surfactant 0.3 parts (Product name: SWAM AM-2150, manufactured by Nippon Surfactant)

<Recording Sheet 2> The amount of polyvinyl alcohol in the recording sheet 1 was increased to 46 parts.

<Recording sheet 3> To the ink receiving layer of recording sheet 1 was added 10 mmol / m ² of a compound represented by the following formula (10).

<Recording Sheet 4> To the ink receiving layer of the recording sheet 1 was added 10 mmol / m ² of a compound represented by the following formula (11).

<Recording Sheet 5> To the ink receiving layer of the recording sheet 1, 10 mmol / m ^{2 was} added.

<Recording Sheet 6> Ascorbic acid was added to the ink receiving layer of the recording sheet 1 in an amount of 10 mmol / m ² .

<Recording Sheet 7> The compound A-1 of the present invention was added to the ink receiving layer of the recording sheet 1 in an amount of 10 mmol / m ² .

<Recording Sheet 8> Compound A-7 of the present invention was added to the ink receiving layer of recording sheet 1 in an amount of 10 mmol / m ² .

<Recording Sheet 9> To the ink receiving layer of the recording sheet 1, 10 mmol / m ² of the compound B-4 of the present invention was added.

<Recording Sheet 10> Compound B-9 of the present invention was added to the ink receiving layer of recording sheet 1 in an amount of 10 mmol / m ² .

<Recording Sheet 11> To the ink receiving layer of recording sheet 1, 10 mmol / m ² of the compound C-1 of the present invention was added.

[0088]

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[0089]

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[0090]

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Each of the obtained ink jet recording sheets was evaluated for ink absorbency, storage stability after printing (light fastness and gas fastness), and gloss. Table 1 shows the results.

<Ink Absorption> Using an ink-jet printer (PM-770C manufactured by Seiko Epson Corporation),
Print 100% of each of C, M, Y, and PP immediately after printing
The C paper was superimposed on the printing portion and pressed lightly, and the amount of ink transferred to the PPC paper was visually observed and evaluated according to the following criteria. ：: No transfer at all. ×: Transfer.

<Light resistance> CYMK using an ink jet printer (PM-770C manufactured by Seiko Epson Corporation) was used.
Solid printing was performed with each of the above inks, and irradiation was performed at 600 W / m ² for 30 hours using a Suntest CPS photobleaching tester manufactured by Atlas Co., Ltd., and the density of the printed area was measured. Of the CMYK images, and the image with the lowest remaining rate among the CMYK images was displayed.

<Gas Resistance> After printing in the same manner as in the light resistance test described above, after exposure to air at room temperature for 3 months, the density of the printed portion was measured, and the image residual ratio (density after exposure / density before exposure) was measured. ) Was obtained, and among the CMYK images, the one with the lowest remaining rate was displayed.

<Glossiness> Glossiness was measured according to the method described in JIS P-8142 (Test method for 75 ° specular glossiness of paper and paperboard).

[0096]

[Table 1] 記録 Recording sheet Ink absorptivity Storage (%) Remarks Lightfastness Gasfastness ───────────────────────────── 1 ○ 70 68 comparison 2 × 72 80 comparison 3 ○ 78 70 comparison 4 ○ 77 72 comparison 5 ７６ 76 71 Comparison 6 ７５ 75 73 Comparison 7 本 82 92 Invention 8 ８２ 82 90 Invention 9 ８４ 84 93 Invention 10 ８２ 82 91 Invention 11 ８１ 81 86 Invention ─────────── ─────────────────

The gloss was 60 to 6 for all recording sheets.
5% showed high gloss.

As is evident from the above results, the use of the compound of the present invention improves storage stability while maintaining high ink absorption. That is, although the ink absorbency is improved by reducing the amount of the polyvinyl alcohol which is a water-soluble binder, the storage stability, particularly the gas resistance, is significantly reduced. According to the present invention, the ink absorbency and the storage stability are improved at the same time, and a photo-like high gloss can be obtained.

Example 2 The fumed silica used in Example 1 had an average primary particle size of 30 n.
The same test was conducted except that m was replaced. As a result, almost the same results were obtained in the ink absorbency and the storage stability, but the glossiness was reduced by 5 to 10%.

Example 3 The recording sheets 7 to 11 of the present invention of Example 1 were further added with a diallylamine hydrochloride-sulfur dioxide copolymer (trade name PAS-92, manufactured by Nitto Boseki) as a cationic compound. The recording sheets 7A to 11A and 7B are prepared using three parts of basic polyaluminum hydroxide (Hyurachem WT manufactured by Riken Clean Co., Ltd.).
11B was prepared and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0101]

[Table 2] ────────────────────────────── Recording sheet Cationic ink absorptivity Storage compound Light fastness Gas fastness ７ 7A PAS-92 ○ 83 948 A 〃 ○ 83 939 A 〃 ○ 84 94 10A 〃 ○ 81 94 11A 〃 ８２ 82 907B Hydrachem WT ９２ 92 978B 〃 ９２ 92 97 9B 〃 ９１ 91 98 10B 〃 ───────────────── 90 96 11B 〃 ９１ 91 91 ───────────────── ─────────────

The gloss was 60 to 6 for all recording sheets.
5% showed high gloss.

As can be seen from the above results, the storage stability is further improved by using the compound of the present invention in combination with a cationic polymer or a water-soluble metal compound as the cationic compound.

Example 4 As a support, LBKP (50 parts) and LBSP (50 parts) were used.
Part) of a pulp blend of 120 g / m ^{2 and} a resin composition comprising low-density polyethylene (70 parts), high-density polyethylene (20 parts) and titanium oxide (10 parts) applied to the surface of 25 g / m ^2. And high-density polyethylene (50
Parts) and a low-density polyethylene (50 parts) resin coating paper prepared by applying 25 g / m ² .

An ink receiving layer coating solution having the following composition was prepared on the above support, and the coating amount of fumed silica was 18 g in solid content.
/ M ² and dried to prepare an ink jet recording sheet. In addition, all the recording sheets were adjusted so that the film surface pH of the ink receiving layer became 4.2.

<Recording sheet 21> 100 parts of fumed silica (average primary particle size: 7 nm, specific surface area by BET method: 300 m ² / g) 23 parts of polyvinyl alcohol (trade name: PVA235, manufactured by Kuraray Co., Ltd., degree of saponification) 88%, average polymerization degree 3500) Boric acid 4 parts Amphoteric surfactant 0.3 parts (Product name: SWAM AM-2150, manufactured by Nippon Surfactant)

<Recording Sheet 22> Maltose was added to the ink receiving layer of the recording sheet 21 at 12 mmol / m ² .

<Recording Sheet 23> To the ink receiving layer of the recording sheet 21, 12 mmol / m ² of the compound A-1 of the present invention was added.

<Recording Sheet 24> To the ink receiving layer of the recording sheet 21, 12 mmol / m ² of the compound A-7 of the present invention was added.

<Recording Sheet 25> To the ink receiving layer of the recording sheet 21, 12 mmol / m ² of the compound B-4 of the present invention was added.

<Recording Sheet 26> To the ink-receiving layer of the recording sheet 21, 12 mmol / m ² of the compound B-9 of the present invention was added.

<Recording Sheet 27> Compound C-1 of the present invention was added to the ink receiving layer of recording sheet 21 at 12 mmol / m ² .

[0113] <Recording sheet 28> Compound A-1 6 mmol / m ² of the present invention in the ink receiving layer of the recording sheet 21, and N- methylthiourea were added 6 mmol / m ^2.

[0114] <Recording sheet 29> Compound A-1 6 mmol / m ² of the present invention in the ink receiving layer of the recording sheet 21, and maltose were added 6 mmol / m ^2.

[0115] <Recording sheet 30> Compound A-1 6 mmol / m ² of the present invention in the ink receiving layer of the recording sheet 21, and isonicotinate was added 6 mmol / m ^2.

[0116] <Recording sheet 31> Compound A-1 of the present invention 6 mmol / m ^2, and 3,6-dithio-1,8-octanediol to 6 mmol / m ² applied to the ink-receiving layer of the recording sheet 21 Was.

[0117] <Recording sheet 32> Compound A-1 6 mmol / m ² of the present invention in the ink receiving layer of the recording sheet 21, and DL-alpha-lipoic acid was added 6 mmol / m ^2.

<Recording Sheet 33> The compound A-1 of the present invention was added to the ink receiving layer of the recording sheet 21 in an amount of 6 mmol / m ² ,
And 5,6-dihydro- (4H) -1,3-thiazine-
6 mmol / m ^{2 of} 2-thiol was added.

With respect to each of the obtained ink jet recording sheets, the ink absorption, the storage stability after printing (light fastness and gas fastness), and the gloss were evaluated in the same manner as in Examples 1 to 3. Table 3 shows the results.

[0120]

[Table 3] 記録 Recording sheet Ink absorptivity Storage (%) Remarks Lightfastness Gasfastness ───────────────────────────── 21 ○ 70 67 Comparison 22 △ 81 83 Comparison 23 ○ 83 91 Invention 24 ○ 83 91 Invention 25 ○ 84 93 Invention 26 ○ 82 92 Invention 27 ○ 81 87 Invention 28 ○ 84 95 Invention 29 ○ 85 97 Invention 30 ○ 84 95 Invention 31 ○ 85 97 Invention 32 ○ 84 96 Invention 33 ○ 85 95 The present invention ────────────────────────────

The gloss was 60 to 6 for all recording sheets.
5% showed high gloss.

As is clear from the above results, the second aspect of the present invention
The recording sheets 28 to 33 using the kinds of compounds have further improved storage stability than the recording sheets 23 to 27 using one kind of the compounds of the present invention, while maintaining high ink absorbency. In addition, the recording sheet 22 using the saccharide alone had lower ink absorbency than the recording sheet 21 not added, and the effect of improving the gas resistance was insufficient.

Example 5 The recording sheets 28 to 33 of the present invention of Example 4 were further added with cationic compounds such as diallylamine hydrochloride-sulfur dioxide copolymer (trade name PAS-92, manufactured by Nitto Boseki Co., Ltd.) and The recording sheets 28A to 33A, 2 were prepared using three parts of basic polyaluminum hydroxide (Hyurachem WT manufactured by Riken Clean Co., Ltd.).
8B to 33B were prepared and evaluated in the same manner as in Example 4. Table 4 shows the results.

[0124]

[Table 4] ────────────────────────────── Recording sheet Cationic ink absorptivity Storage compound Light fastness Gas fastness ２８ 28A PAS-92 ○ 84 97 29A 〃 ○ 85 99 30A 〃 ○ 85 96 31A 〃 ○ 85 99 32A ○ ○ 85 98 33A ○ ○ 86 97 28B Hydrachem WT ○ 94 97 29B ○ ○ 95 9930B ○ ○ 95 96 31B ○ ○ 94 98 32B ○ ○ 95 97 33B ○ ○ 95 98 98 ───────────────────────

The degree of gloss was 60 to 6 for all recording sheets.
5% showed high gloss.

As can be seen from the above results, the use of a compound of the present invention in combination with a cationic polymer or a water-soluble metal compound as a cationic compound particularly improves the gas storage stability.

[0127]

According to the present invention, a photo-like ink jet recording material having high ink absorption, high gloss and improved storage stability can be obtained.

Claims (18)

[Claims] 1. An ink jet recording material having an ink receiving layer containing inorganic fine particles provided on a support, wherein the ink receiving layer has at least one selected from a sulfinic acid compound, a thiosulfonic acid compound, and a thiosulfinic acid compound. An ink-jet recording material comprising a compound. 2. In an ink jet recording material having an ink receiving layer containing inorganic fine particles provided on a support, the ink receiving layer comprises at least one of (A) a sulfinic acid compound, a thiosulfonic acid compound, and a thiosulfinic acid compound. And (B) a thiourea compound, (C) a saccharide,
An ink jet recording material containing at least one compound selected from the group consisting of (D) a pyridine compound, (E) a thioether compound, (F) a disulfide compound, and (G) a thiazine compound. 3. The ink jet recording material according to claim 2, wherein the thiourea-based compound of the compound (B) is at least one compound having at least one structure represented by the following general formula (1) in the molecule. . Embedded image 4. The thioether compound of the compound (E) is at least one of the compounds represented by the following general formula (2).
3. The ink jet recording material according to claim 2, wherein Embedded image [In the general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, or an aromatic group, and R ₁ and R ₂
May be the same or different, and may combine to form a ring. At least one of R ₁ and R ₂ is an alkyl group substituted with a hydrophilic group such as an amino group, an amide group, an ammonium group, a hydroxy group, a sulfo group, a carboxy group, an aminocarbonyl group or an aminosulfonyl group, or an aromatic group. Group. R ₃ may be substituted, and in some cases represents an alkylene group having an oxygen atom. m represents a positive number of 0 to 10. When m is 1 or more, at least one sulfur atom bonded to R ₃ may be a sulfonyl group. ] 5. The disulfide compound of the compound (F) is at least one of the compounds represented by the following general formula (3).
3. The ink jet recording material according to claim 2, wherein Embedded image [In the general formula (3), R ₁ and R ₂ are each an organic group containing a carbon atom or a nitrogen atom bonded to a sulfur atom of disulfide. This organic group forms a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocyclic group together with a carbon or nitrogen atom bonded to the sulfur atom of the disulfide. Even if it is, an aliphatic group, an aromatic group, a heterocyclic group or an amino group substituted or unsubstituted at a carbon atom or a nitrogen atom bonded to a sulfur atom of disulfide, and an imino group, an oxygen atom, a yellow atom And the like may be an organic group bonded thereto. R ₁ and R ₂ may be the same or different, and may combine to form a ring. The above substituents for R ₁ and R ₂ are an alkyl group, an aryl group, a heterocyclic group, an amino group, an amide group, an imino group, an ammonium group,
It is a substituent such as a hydroxy group, a sulfo group, a carboxy group, an aminocarbonyl group or an aminosulfonyl group, and a halogen atom. ] 6. The ink jet recording material according to claim 2, wherein the thiazine compound of the compound (G) is at least one of a mercaptothiazine compound. 7. The ink jet recording material according to claim 2, wherein the water-soluble polyvalent metal salt of the compound (B) is at least one of nickel, zinc and cobalt. 8. The thiourea-based compound of the compound (B) is thiourea, N-methylthiourea, N-acetylthiourea, 1,3-diphenylthiourea, tetramethylthiourea, guanylthiourea, 4-methylthiosemicarbazide, 1,3 -Bis (hydroxymethyl)-
2 (3H) benzimidazolethione, 6-hydroxy-1-phenyl-3,4-dihydropyrimidine-2 (1
H) -Thion, 1-allyl-2-thiourea, 1,3-
3. The ink jet recording material according to claim 2, which is at least one of dimethyl-2-thiourea, 1,3-diethyl-2-thiourea, ethylenethiourea, and trimethylthiourea. 9. The ink-jet recording material according to claim 2, wherein the saccharide of the compound (C) is at least one of reducing saccharides. 10. The pyridine compound of the compound (D) is 4-aminomethylpyridine, 4-chloropyridine hydrochloride, 4-hydroxypyridine, 4-cyanopyridine,
The ink jet recording material according to claim 2, wherein the material is at least one of 3-cyanopyridine, 2,2'-bipyridine, isonicotinamide, and methyl isonicotinate. 11. The thioether compound of the compound (E) is 3,6-dithio-1,8-octanediol,
It is at least one of bis [2- (2-hydroxyethylthio) ethyl] sulfone, 3,6,9-trithio-1,11-undecanediol, 4- (methylthio) phenol, and 2- (phenylthio) ethanol. Item 6. An ink jet recording material according to item 4. 12. The method according to claim 2, wherein the disulfide compound of the compound (F) is at least one of DL-α-lipoic acid, 4,4′-dithiodimorpholine, and 4,4′-dithiodibutanoic acid. The ink-jet recording material as described above. 13. The thiazine compound of the compound (G) is 5,6-dihydro- (4H) -1,3-thiazine-
2-thiol, 3-benzyl-1,3-thiazinane-2
-Thione, 3-methyl-1,3-thiazinane-2-thione, 5,6-dihydro-2-methylthio-4H-1,3
7. The ink jet recording material according to claim 6, which is at least one of -thiazine and 3-carboxymethyl-6,6-dimethyl-4-oxo-1,3-thiazinane-2-thione. 14. The ink jet recording material according to claim 1, wherein the support is a support in which both sides of a base paper are coated with a polyolefin resin. 15. The ink receiving layer contains 10 inorganic fine particles.
To 30 g / m ² containing ink jet recording material according to any one of claims 1 to 14, a hydrophilic binder to the inorganic fine particles, containing 30 wt% or less. 16. The ink jet recording material according to claim 1, wherein the inorganic fine particles are fumed silica. 17. The primary particle of the fumed silica has an average particle diameter of 3 to 15 nm and a specific surface area of 2% by a BET method.
17. The ink jet recording material according to claim 16, which is not less than 00 m ² / g. 18. The ink jet recording material according to claim 1, wherein the ink receiving layer further contains a cationic compound.