JP2002240421A - Inkjet recording materials - Google Patents

Abstract

(57) Abstract: Provided is an ink jet recording material having improved photo-like high gloss, high ink absorption, and storage stability. In an ink jet recording material having an ink receiving layer provided on a support, the ink receiving layer has a urea structure in which at least one of an etheric oxygen atom and a sulfonyl group is directly bonded to at least one nitrogen atom. A compound having a urea structure to which a hindered phenol or hindered amine structure is bonded, a compound represented by the general formula [III], and three or more urea structures which may have a substituent in the same molecule. An ink jet recording material comprising at least one compound among the compounds. Embedded image

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, and more particularly, to a photo-like high gloss,
The present invention relates to an ink jet recording material having excellent ink absorbency and improved storage stability after printing.

[0002]

2. Description of the Related Art The ink jet recording method is a printing method in which small droplets of an ink composition fly and adhere to a recording medium such as paper to perform printing. This method has a feature that high-resolution and high-quality images can be printed at a high speed with a relatively inexpensive device. When a color image is formed using an inkjet recording method, at least the three primary colors of yellow ink, magenta ink, and cyan ink are mainly used. However, light and dark inks having different densities are used for magenta ink and cyan ink, respectively. There is also a method of obtaining a higher definition image. In general, an ink composition used for ink jet recording mainly contains water, and further contains a coloring component and a wetting agent such as glycerin for the purpose of preventing clogging.

[0003] Ink jet recording inks are required to have water resistance because the coloring material may be dissolved or dispersed again when the obtained image comes into contact with water. For example, Japanese Patent Application Laid-Open No. A method of adding a cationic polymer as described in JP-A-2-296778, JP-A-2-255876, JP-A-3-188174, JP-A-7-305011, and the like is known. In addition, it is important that the ink for ink jet recording not only has excellent storability of the coloring material in the ink, but also has excellent storability such as light resistance and gas resistance of the obtained image. In particular, when a color image is printed, if any one of the plurality of colors has poor storage stability, the hue changes and the quality of the color image is extremely deteriorated. Further, when a high-definition image is printed by using the dark and light ink, there is a problem that the deterioration is remarkable particularly in an image area using the dark and light ink. Therefore, excellent preservability is required for printed materials of photographic specifications and printed materials exposed to direct sunlight such as outdoors.

On the other hand, as a recording material used in the ink jet recording system, a porous material comprising a pigment such as amorphous silica and a water-soluble binder such as polyvinyl alcohol is provided on a support called ordinary paper or ink jet recording paper. There is known a recording material provided with an ink absorbing layer.

[0005] For example, JP-A-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.

[0006] 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 ultrafine particles such as fumed silica has a problem that a printed image is easily discolored during storage after printing. That is,
There was a major problem in that discoloration due to light and trace gases in the atmosphere was likely to occur. Numerous proposals have been made for the goal of suppressing such discoloration and fading and improving the storability of a printed image. For example, JP-A-57-74193, JP-A-57-87988 and JP-A-57-87988
No. 2-261478 discloses a method using an ultraviolet absorber,
Also, JP-A-57-74192 and JP-A-57-87989.
No. 60-72785, No. 61-146591,
JP-A-62-170381, JP-A-62-61477, JP-A-3-13376, JP-A-7-314881, and JP-A-7-3
No. 14882, No. 8-25796, No. 9-26754
No. 4, etc., describe a method using an antioxidant or an anti-fading agent. However, all of these methods have an inadequate effect of preventing discoloration and fading, or even having the effect of preventing discoloration, such as coloring itself or discoloring the recording dye immediately after printing. At present, it has not reached a sufficient level of practical use. As described above, in ink-jet recording materials having a porous ink-receiving layer, the storability of this printed image is a particularly important issue, and urgent measures have been desired.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ink-jet recording material having excellent preservability of a printed portion,
And an inkjet recording method,
In particular, it is an object of the present invention to provide an ink jet recording material having a porous ink receiving layer having high photo-like gloss and high ink absorption.

[0010]

The object of the present invention is at least one of an etheric oxygen atom and a sulfonyl group directly bonded to at least one nitrogen atom, preferably represented by the general formula [I]. A compound having a urea structure,
Compound having a urea structure preferably having a hindered phenol or hindered amine structure, preferably represented by the general formula [II], a compound represented by the general formula [III], and urea optionally having a substituent An ink-jet recording material provided on a support provided an ink-receiving layer containing at least one of compounds having three or more structures in the same molecule.

[0011]

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[0012]

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[0013]

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In the general formula [I], R ₁ and R ₂ represent a hydrogen atom, an optionally substituted alkyl group, alkenyl group, aralkyl group, aryl group or heterocyclic group;
X represents OR ₁₁ or SO ₂ R _12. Where R ₁₁ and R ₁₂
Is an alkyl group, alkenyl group, aralkyl group, aryl group or heterocyclic group which may have a substituent.
In the general formula [II], R ₃ and R ₄ represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and L ₁ is a divalent link The group, n is 0 or 1, and Z is a hindered phenol or hindered amine structure. In the general formula [III], R _{5 to} R ₁₀ represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and L ₂ represents two nitrogen atoms Represents a divalent linking group in which the shortest linking moiety connecting the two has 2 or more carbon atoms. R ₅ and R ₆ or R ₉ and R ₁₀ may combine to form a ring structure, and R ₇ and R ₈ may combine to form a ring structure with two nitrogen atoms and L _2. You may.

Specific examples of R ₁ and R ₂ include a hydrogen atom, a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-sulfoethyl group, a 2-carboxyethyl group, and a 2- (2-hydroxyethoxy) ethyl group. , 2,3-dihydroxypropyl, 2- (2-methoxyethoxy) ethyl, allyl, methallyl, benzyl, p-hydroxybenzyl, phenyl, p-carboxyphenyl, thienyl, furyl, etc. Can be mentioned. Specific examples of R ₁₁ and R ₁₂ include a methyl group, an ethyl group, a 2-hydroxyethyl group, an allyl group, a methallyl group, a benzyl group, a p-methylphenyl group, and a pyridyl group.
Among these, at least one of R ₁ and R ₂ is preferably an alkyl group having a hydrophilic group such as a hydroxy group, a sulfo group, a carboxy group, or a (poly) ethyleneoxy group as a substituent. In the compound having the partial structure of the general formula [I], the number of [I] to be contained is not particularly limited, but the solubility in a solvent when added to the ink receiving layer and the crystal precipitation from the receiving layer From the viewpoint of preventing the above, 1 to 3 are preferable.

Specific examples of R ₃ and R ₄ include a hydrogen atom, a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-sulfoethyl group, a 2-carboxyethyl group and a 2- (2-hydroxyethoxy) ethyl group. , 2,3-dihydroxypropyl, 2- (2-methoxyethoxy) ethyl, allyl, methallyl, benzyl, p-hydroxybenzyl, phenyl, p-carboxyphenyl, thienyl, furyl, etc. Can be mentioned. Specific examples of L ₁ include a 1,2-ethanediyl group and a 1,3-propanediyl group. The hindered phenol or hindered amine structure represented by Z indicates the structure of a group of compounds well known as an antioxidant or a light stabilizer in the field of additives for plastics. For example,
Pages 1039 to 1043 or 1054 of Chemical Daily, Inc.
The compound group described on the page has in common,
A phenol structure having a sterically bulky substituent such as a t-butyl group in at least one adjacent position, and a nitrogen-containing 6-membered ring structure in which both sides of a nitrogen atom are all alkyl-substituted can be mentioned. Specific examples include a 2,6-di-t-butylphenol structure, a 2,6-di-t-butyl-p-cresol structure, and 4,4′-methylenebis (2,
6-di-t-butylphenol) structure, 2,2,6,6
-Tetramethylpiperidine structure, 1,2,2,6,6-
Examples thereof include a pentamethylpiperidine structure.
Among these, it is preferable that Z has a hindered amine structure. In the compound having the partial structure of the general formula [II], the number of [II] to be contained is not particularly limited, but the solubility in a solvent when added to the ink receiving layer and the precipitation of crystals from the receiving layer. From the viewpoint of preventing the above, 1 to 3 are preferable.

Specific examples of R _{5 to} R ₁₀ include a hydrogen atom,
Methyl group, ethyl group, 2-hydroxyethyl group, 2-sulfoethyl group, 2-carboxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, 2- (2-methoxyethoxy) ethyl, allyl, methallyl, benzyl, p- hydroxybenzyl group, a phenyl group, p- carboxyphenyl, thienyl group, and a furyl group, etc., specific examples of L ₂ is 1,2 -An ethanediyl group, a 1,3-propanediyl group, a 1,6-hexanediyl group, a 1,3-xylylenediyl group, and the like. Specific examples of the ring structure formed by combining R ₅ and R ₆ or R ₉ and R ₁₀ include structures such as a pyrrolidine ring, a piperidine ring, and a morpholine ring, including the nitrogen atom to which they are bonded. Specific examples of the ring structure formed by combining R ₇ and R ₈ together with two nitrogen atoms and L ₂ include a piperazine ring. Among them, R ₅ ~
At least one of R ₁₀ is preferably an alkyl group having a hydrophilic group such as a hydroxy group, a sulfo group, a carboxy group, or a (poly) ethyleneoxy group as a substituent.

The urea structure which may have a substituent is
N-C with hydrogen or carbon bonded to both nitrogens
Refers to an ON structure. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom, a hydroxy group, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, an amino group such as a dimethylamino group, a carboxy group, and an ester. And aromatic or heterocyclic groups such as a group, an amide group, a sulfo group, a phenyl group, a thienyl group, and a furyl group. Among them, hydrophilic substituents such as a hydroxy group, a sulfo group and a carboxy group are preferred.

Next, specific examples of the above-mentioned compounds used in the recording material of the present invention are shown below, but the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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The preferred ink jet recording material of the present invention is one in which the ink is absorbed in the voids formed in the film by the inorganic 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 inorganic fine particles on the support, and the amount of the hydrophilic binder is preferably reduced in order to increase the porosity. Examples of the inorganic fine particles used in the present invention include various known fine particles such as silica and alumina, and silica is particularly preferable. The ink receiving layer preferably contains 8 g / m ² or more of inorganic fine particles,
More preferably, it is used in the range of 10 to 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 10 to 40% by weight with respect to the inorganic fine particles. By reducing the ratio of the hydrophilic binder in this manner, the ink absorbency is improved, but the storage stability after printing, particularly gas resistance, tends to decrease, and the present invention is intended to satisfy these performances simultaneously. Features.

In the present invention, the inorganic fine particles constitute the main proportion in the ink receiving layer, that is, 50% by weight or more, preferably 60% by weight or more, more preferably 65% by weight based on the total solid content of the ink receiving layer. It is preferable to contain the above.

[0027] 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 with respect 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 Corporation.
It is commercially available as the S type and can be obtained.

The average particle diameter 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 inorganic fine particles, various known binders can be used, but a hydrophilic binder which has high transparency and can obtain higher permeability of the ink is preferably used. 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 degree of saponification 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 No. 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 (hardener) 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, 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, U.S. Pat.
No. 5,718, compounds having reactive olefins, N-methylol compounds as described in U.S. Pat. No. 2,732,316, isocyanates as described in U.S. Pat. No. 3,103,437, U.S. Pat. 3,017,28
0, 2,983,611; aziridine compounds as described in U.S. Pat. No. 3,100,704; carbodiimide-based compounds as described in U.S. Pat. No. 3,100,704;
No. 7, such as epoxy compounds, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, and inorganic crosslinking agents such as chrome alum, zirconium sulfate, boric acid and borate. It can be used in combination of more than one kind. Among these, boric acid or borate is particularly preferred.

According to the present invention, at least one of an etheric oxygen atom and a sulfonyl group is directly bonded to at least one nitrogen atom in combination with inorganic fine particles, particularly fumed silica, and preferably represented by the general formula [I]. A compound having a urea structure represented by the general formula [II], a compound having a urea structure represented by the general formula [II], a compound having a hindered phenol or hindered amine structure bonded thereto, and a substituent By containing at least one of the compounds containing three or more urea structures which may have the same molecule in the same molecule, the storage stability after printing of the ink jet recording material is remarkably improved.

The content of the above compound in the ink receiving layer is preferably 0.1 to 50 mmol / m ^2, more preferably 0.2 to 50 mmol / m ^2.
20 mmol / m ² is more preferred.

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.

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

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 amide sulfate 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 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 tungsten citrate, 12 tungstophosphate n Hydrate, 12-tungstosilicic acid 26-hydrate, molybdenum chloride, 12-molybdophosphate n-hydrate and the like.

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 formula A, B or C. For example, [Al ₆ (OH) ₁₅ ] ³⁺ , [Al ₈ (OH) ₂₀ ] ^{4 +} , [A
^{_{l 13 (OH) 34] 5+}} , a _{[Al 21 (OH) 60]} 3+, water-soluble poly aluminum hydroxide with a basic contain polynuclear condensed ions of a polymer stable as the like.

[Al ₂ (OH) _n Cl _6-n ] _m Formula A [Al (OH) ₃ ] _n AlCl ₃ Formula B Al _n (OH) _m Cl _(3n-m) 0 <m <3n Formula C

These are water treatment agents under the name of polyaluminum chloride (PAC) from Taki Kagaku 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 of 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 such as zirconium acetate, zirconium chloride, zirconium oxychloride, zirconium hydroxychloride, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, ammonium zirconium carbonate, potassium zirconium 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 above-mentioned water-soluble metal compound in the ink receiving layer is 0.1 to the inorganic fine particles.
The content is preferably 1 to 10% by weight, more preferably 1 to 5% by weight.

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

In the present invention, the surface pH of the ink receiving layer containing the inorganic fine particles is preferably from 2 to 6,
Particularly, 3 to 5 are preferable. The surface pH of the ink receiving layer is
J. According to the method described in TAPPI paper pulp test method N0.49, the surface p measured using distilled water after 30 seconds.
H.

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 the 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, and 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 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. However, it is preferable that the base paper has good surface smoothness, for example, by applying a pressure by a calender or the like during or after paper making, 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 curable 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, which is 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, both surfaces of which are formed 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, the ink jet recording material may be provided with an ink absorbing layer, an ink fixing layer, an intermediate layer, a protective layer and the like in addition to the layer containing inorganic fine particles. 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.

The ink composition suitably used for the ink jet recording material of the present invention is not particularly limited. For example, JP-A Nos. 9-151345 and 9-1.
65539 and 10-259334 can be used.

As the dye of the ink composition, known direct dyes, acid dyes, food dyes, basic dyes, reactive dyes,
Disperse dye, vat dye, soluble vat dye, reactive disperse dye,
Any of oil-based dyes and the like can be used, and among them, water-soluble dyes are preferably used in terms of the performance of the recording liquid. Further, among these dyes, the direct dye having relatively poor storage stability after printing has a remarkable effect of improving the image storage stability of the present invention.

As the solvent for the ink composition, water and an organic solvent are used. In particular, as the organic solvent, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε Nitrogen-containing cyclic compounds such as caprolactam, and mixtures thereof, and ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Polyhydric alcohols such as 1,3-propanediol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerin, and mixtures thereof are preferred.

In the ink composition, a nonionic acetylene glycol-based surfactant such as Surfynol 465, Surfynol 104, Olfin STG (trade name, manufactured by Nissin Chemical Co., Ltd.), etc. Glycol ethers such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol monoethyl ether may be used. Further, as a pH adjuster, tri (hydroxyalkyl) amine such as triethanolamine, LiOH, A hydroxide of a metal element selected from the group consisting of group Ia elements such as NaOH and KOH can be used. If necessary, lower alcohols,
A water-soluble polymer such as sodium alginate, a water-soluble resin, a fluorinated surfactant, a fungicide, a rust preventive, and the like may be added.

[0066]

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 25 g / m ² resin composition comprising low-density polyethylene (70 parts), high-density polyethylene (20 parts) and titanium oxide (10 parts) is applied to the surface of a 120 g / m ² base paper. 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> Vapor-phase method silica (average primary particle diameter 7 nm, specific surface area by BET method 300 m ² / g) 100 parts Polyvinyl alcohol 25 parts (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> To the ink receiving layer of the above-mentioned recording sheet 1, a compound of the following formula 12 was added at 5 mmol / m ² .

<Recording Sheet 3> To the ink-receiving layer of the above-mentioned recording sheet 1, 5 mmol / m ² of the following compound was added.

<Recording Sheet 4> To the ink receiving layer of the recording sheet 1 was added 5 mmol / m ^{2 of the following} compound (14).

<Recording Sheet 5> To the ink receiving layer of the above-mentioned recording sheet 1 was added 5 mmol / m ² of a compound represented by the following formula (15).

<Recording Sheet 6> The compound (2) of the present invention was added to the ink receiving layer of the recording sheet 1 in an amount of 5 mmol / m ² .

<Recording Sheet 7> The compound (4) of the present invention was added to the ink receiving layer of the recording sheet 1 in an amount of 5 mmol / m ² .

<Recording Sheet 8> The compound (6) of the present invention was added to the ink receiving layer of the recording sheet 1 in an amount of 2.5 mmol / m ^2.
added.

<Recording Sheet 9> The compound (12) of the present invention was added to the ink receiving layer of the recording sheet 1 in an amount of 3.3 mmol / l.
m ² were added.

<Recording Sheet 10> The compound (15) of the present invention was added to the ink receiving layer of the recording sheet 1 in an amount of 2.5 mmol / m ² .

<Recording Sheet 11> The compound (18) of the present invention was added to the ink receiving layer of the recording sheet 1 in an amount of 5 mmol / m ^2.
added.

<Recording Sheet 12> To the ink receiving layer of the above-mentioned recording sheet 1, 2.5 mmol / m ² of the compound (21) of the present invention was added.

<Recording Sheet 13> The compound (24) of the present invention was added to the ink receiving layer of the recording sheet 1 in an amount of 2.5 mmol / m ² .

<Recording Sheet 14> To the ink receiving layer of the above-mentioned recording sheet 1, 3.3 mmol / m ² of the compound (28) of the present invention was added.

<Recording Sheet 15> To the ink receiving layer of the above-mentioned recording sheet 1, 3.3 mmol / m ² of the compound (30) of the present invention was added.

[0084]

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[0085]

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[0086]

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[0087]

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For each of the obtained ink jet recording sheets, a six-color ink jet printer (PM-770 manufactured by Seiko Epson Corporation) using the following dark and light inks was used.
C) was used to evaluate the ink absorbency, storage stability after printing (light fastness and gas fastness), and gloss. Table 1 shows the results.

<Ink Absorbability> C, M and Y were each 1
Immediately after printing, PPC paper was superimposed on the printed portion and lightly pressed, 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.

<Gas resistance> Solid printing was performed so that the optical density of cyan with the greatest fading was 1.0, and after exposure to air at room temperature for 3 months, the optical density of the printed portion was measured. Residual rate (optical density after exposure / optical density before exposure)
And the results are shown in Table 1.

<Lightfastness> Solid printing was performed so that the optical density of cyan became 1.0 in the same manner as in the above gasfastness test, and a 6-color photobleaching tester manufactured by Atlas Suntest CPS was used.
After irradiation at 00 W / m ² for 30 hours, the optical density of the printed portion was measured, and the residual ratio (optical density after irradiation / optical density before irradiation)
And the results are shown in Table 1.

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

The composition of the dark and light inks used is as follows.

[Cyan Ink] Direct Blue 199 2.4 g Ethylene glycol 16.01 g Glycerin 9.5 g Finished to 100 ml with pure water.

[Magenta Ink] Direct Red 227 1.8 g Glycerin 3.5 g Diethylene glycol monobutyl ether 21.5 g Finished to 100 ml with pure water.

[Yellow Ink] Direct Yellow 86 2.0 g Diethylene glycol 22.2 g Glycerin 4.5 g Finished to 100 ml with pure water.

[Light Cyan Ink] Direct Blue 199 0.6 g Ethylene glycol 16.01 g Glycerin 9.5 g Finished to 100 ml with pure water.

[Light Magenta Ink] Direct Red 227 0.5 g Glycerin 3.5 g Diethylene glycol monobutyl ether 21.5 g Finished to 100 ml with pure water.

[0099]

[Table 1] 記録 Recording sheet Ink absorptivity Storage (%) Remarks Lightfastness Gasfastness ───────────────────────────── 1 ○ 65 68 Comparison 2 ○ 68 70 Comparison 3 ○ 70 71 Comparison 4 ○ 71 73 Comparison 5 ○ 7275 Comparison 6 ○ 81 84 Invention 7 ○ 80 82 Invention 8 ○ 85 85 Invention 9 ○ 86 87 Invention 10 ○ 83 93 Invention 11 ○ 79 90 Invention 12 ○ 86 91 Invention 13 ○ 84 89 The present invention 14 ○ 88 92 The present invention 15 ○ 87 92 The present invention ────────────────────────────

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

Example 2 The recording sheets 1 to 15 of Example 1 were similarly subjected to ink absorption and printing after printing using a four-color ink jet printer (PM-900C manufactured by Seiko Epson Corporation) using the following dark ink. The storability (light resistance and gas resistance) and gloss were evaluated. Table 2 shows the results.

The composition of the dark ink used is as follows.

[Cyan Ink] Direct Blue 199 2.4 g Ethylene glycol 16.01 g Glycerin 9.5 g Finished to 100 ml with pure water.

[Magenta Ink] Direct Red 227 1.8 g Glycerin 3.5 g Diethylene glycol monobutyl ether 21.5 g Finished to 100 ml with pure water.

[Yellow Ink] Direct Yellow 86 2.0 g Diethylene glycol 22.2 g Glycerin 4.5 g Finished to 100 ml with pure water.

[0106]

[Table 2] 記録 Recording sheet Ink absorptivity Storage (%) Remarks Lightfastness Gasfastness ───────────────────────────── 1 ○ 70 73 Comparison 2 ○ 74 78 Comparison 3 ○ 76 80 Comparison 4 ○ 78 81 Comparison 5 ○ 7983 Comparison 6 ○ 8588 Invention 7 ○ 84 89 Invention 8 ○ 88 91 Invention 9 ○ 89 92 Invention 10 ○ 8796 Invention 11 ○ 82 92 Invention 12 ○ 88 92 Invention 13 ○ 8791 The present invention 14 ○ 91 93 The present invention 15 ○ 90 93 The present invention ────────────────────────────

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

As is evident from the results in Tables 1 and 2, the use of the compound of the present invention improves storage stability while maintaining high ink absorbency. In particular, when the dark and light inks are used, the effect of improving the storability is particularly remarkable. That is, in the present invention, the ink absorbency and the storage stability are simultaneously improved, and a photo-like high gloss is obtained.

Example 3 The fumed silica used in Example 1 had an average primary particle size of 15 n.
The same test was conducted except that m was replaced. As a result, almost the same results were obtained for the ink absorbency and the storage stability, but the glossiness was reduced by 3 to 6%.

Example 4 The recording sheets 6 to 15 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 Co., Ltd.) as a cationic compound. Recording sheets 6A to 15A were prepared using three parts each of basic polyaluminum hydroxide (Hyurachem WT manufactured by Riken Clean Co., Ltd.) and evaluated in the same manner as in Example 1. Table 3 shows the results.

[0111]

[Table 3] 記録 Recording sheet Ink absorbency Storage (%) Lightfastness Gasfastness ─── ６ 6A ○ 90 867A ○ 91 85 8A ○ 92 889A ○ 93 90 10A ○ 92 96 11A ○ 90 92 12A ○ 93 94 13A ○ 91 92 14A ○ 94 96 15A ○ 93 95 ───────────────────────────

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 compound.

[0114]

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 (14)

[Claims] 1. An ink jet recording material having an ink receiving layer provided on a support, wherein the ink receiving layer has at least one of an etheric oxygen atom and a sulfonyl group directly bonded to at least one nitrogen atom. An ink-jet recording material comprising a compound having a structure. 2. The ink-jet recording according to claim 1, wherein a urea structure in which at least one of the etheric oxygen atom and the sulfonyl group is directly bonded to at least one nitrogen atom is represented by the following general formula [I]. material. Embedded image (In the general formula [I], R ₁ and R ₂ represent a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and X represents OR ₁₁
Or SO ₂ R ₁₂ is shown. Here, R ₁₁ and R ₁₂ are an optionally substituted alkyl group, alkenyl group, aralkyl group, aryl group or heterocyclic group. ) 3. In the general formula [I], at least one of R ₁ and R ₂ is a hydroxy group, a sulfo group, a carboxy group,
3. The ink jet recording material according to claim 2, which is an alkyl group having a hydrophilic group such as a (poly) ethyleneoxy group as a substituent. 4. An ink jet recording material comprising an ink receiving layer provided on a support, wherein the ink receiving layer contains a compound having a urea structure to which a hindered phenol or hindered amine structure is bonded. Recording material. 5. The ink jet recording material according to claim 4, wherein the urea structure having a hindered phenol or hindered amine structure is represented by the following general formula [II]. Embedded image (In the general formula [II], R ₃ and R ₄ represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, and L ₁ is a divalent A linking group, n represents 0 or 1, and Z represents a hindered phenol or hindered amine structure.) 6. The ink jet recording material according to claim 5, wherein in the general formula [II], Z has a hindered amine structure. 7. Ink having an ink receiving layer provided on a support
In a jet recording material, the ink receiving layer generally includes
A compound represented by the formula [III] and a compound having a substituent
Containing three or more urea structures in the same molecule
Characterized in that it contains at least one of
Ink jet recording material. Embedded image(In the general formula [III], R_Five~ R_TenIs a hydrogen atom, substitution
An alkyl group, an alkenyl group,
A alkyl group, an aryl group or a heterocyclic group; _TwoIs two
The shortest linking part connecting two nitrogen atoms has 2 or more carbon atoms
A divalent linking group. R_FiveAnd R₆Or R₉And R_TenIs
R may combine to form a ring structure;₇And R₈Is combined
To obtain two nitrogen atoms and L_TwoForms a ring structure with
It may be. ) 8. In the formula [III], at least one of R _{5 to} R ₁₀ is an alkyl group having a hydrophilic group as a substituent, such as a hydroxy group, a sulfo group, a carboxy group, and a (poly) ethyleneoxy group. The ink-jet recording material according to claim 7, which is provided. 9. The ink jet recording material according to claim 1, wherein said ink receiving layer contains inorganic fine particles. 10. The ink jet recording material according to claim 9, wherein the inorganic fine particles are fumed silica having an average primary particle diameter of 3 to 30 nm. 11. 10 to 40% by weight based on inorganic fine particles
The ink-jet recording material according to claim 9, further comprising a hydrophilic binder. 12. The ink jet recording material according to claim 1, wherein the ink receiving layer is cross-linked by a cross-linking agent. 13. The ink jet recording material according to claim 1, wherein the ink receiving layer further contains a cationic compound. 14. The support according to claim 1, wherein the support is a water-resistant support.
14. The ink-jet recording material according to any one of items 13 to 13.