JPH10264512A - Ink jet recording sheet and recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink jet recording sheet, which is excellent in storability and, at the same time, is lustrous with high quality, by a method wherein a specified compound is added to an ink receiving layer. SOLUTION: In an ink jet recording sheet having one or more ink receiving layers on one side of a support, at least one kind of compounds represented with a formula is included in at least one layer of the ink receiving layers. In the formula, Q<1> and Q<2> represent respectively non-metal atom groups necessary for forming acid unclei and, at the same time, nitrogen-containing heterocyclic groups. Further, L<1> , L<2> and L<3> respectively represent substituted or non- substituted methine groups. M represents a cation. (m) represents an integer of 0 through 4. (n) represents a number necessary for offseting the electric charges in a molecule. The compound is preferably added within the range of 0.01-10 mg/m<2> in the ink receiving layer. As a binder employed in the ink receiving layer, a water-soluble polymer is included. At that time, a gelatine is preferably employed as the water-soluble polymer.

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 sheet using a water-based ink, and more particularly to an ink jet recording sheet having excellent water resistance of a sheet and excellent image resolution and uniformity.

[0002]

2. Description of the Related Art An ink jet recording apparatus (hereinafter, also referred to as an ink jet printer) has low noise, can perform high-speed printing, and can easily perform multicolor recording by using a plurality of ink nozzles. Therefore, in particular, the image information output device using a computer has been rapidly spread in recent years, and its use has been expanded to the production of a color copy or a design image requiring image quality close to a photograph.

[0003] By the way, from the viewpoints of safety and recording characteristics, aqueous inks mainly composed of water and a water-soluble organic solvent are mainly used as inks for ink-jet recording, and ink clogging of nozzles is prevented. Improvements are being made. Further, as a recording sheet, a recording sheet in which a porous ink absorbing layer is provided on a support called ordinary paper or ink jet recording paper has been conventionally used.

However, these recording sheets have not been able to meet the recent demand for high image quality due to the large ink bleeding and low glossiness. Furthermore, when a conventional porous ink absorption layer is used for a film or a glossy resin-coated paper, the surface of the porous ink absorption layer is rough and irregularly reflects light, so that transparency and glossiness are lost. there were. Further, when the ink absorbing layer is non-porous, the light transmittance is improved, but the aqueous ink receiving property is poor,
There is a problem that the ink remains on the sheet surface for a long time after image recording, and the drying and fixing time becomes long.

In order to solve these problems, an ink absorbing layer having high light transmittance and excellent aqueous ink receptivity has been proposed.
It has been proposed to use gelatin. For example, JP-A-62-263084 discloses a receptor layer formed from an aqueous gelatin solution having a specific pH, and JP-A-1-146784 discloses the use of a mixture of gelatin and a surfactant.
Japanese Patent No. 64306 proposes a recording sheet obtained by first converting a coated gelatin into a gel state and then drying the gel by a cold drying method.

The ink receiving layer using these gelatins has excellent ink receptivity and high gloss. However, when stored for a long period of time, it has been found that there is a disadvantage that the hue on the surface of the ink receiving layer changes, especially under high humidity conditions.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a glossy, high quality ink jet recording sheet which is excellent in the preservability of the recording sheet. Second, it is an object of the present invention to provide an ink jet recording sheet having an ink receiving layer having excellent image resolution and uniformity.

[0008]

The present inventors have conducted intensive studies and found that the above object can be achieved by adding a specific compound to the ink receiving layer.

That is, the object of the present invention is achieved by the following constitution.

(1) In an ink jet recording sheet having at least one ink receiving layer on one side of a support, at least one compound represented by the following general formula [I] is used in at least one of the ink receiving layers. An ink jet recording sheet, which is contained in a layer.

[0011]

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[Wherein Q ¹ and Q ² each represent an acidic nucleus and a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic group;
L ¹ , L ² and L ³ each represent a substituted or unsubstituted methine group; M represents a cation; m represents an integer of 0 to 4;
Represents the number required to offset the charge in the molecule. (2) The content of the compound represented by the above general formula [I] in at least one of the ink receiving layers is 0.01 to 10;
mg / m ² , the inkjet recording sheet according to (1), wherein

(3) At least one of the ink receiving layers
(1) characterized in that the layer contains a water-soluble polymer
Or the sheet | seat for inkjet recording of any one of (2).

(4) The ink jet recording sheet according to (3), wherein the water-soluble polymer is selected from gelatins, polyvinylpyrrolidones, polyvinyl alcohols and polyalkylene glycols.

(5) The ink jet recording sheet according to any one of (1) to (4), wherein the support is a hydrophobic substrate.

(6) The ink jet recording sheet according to (5), wherein the hydrophobic substrate is a resin-coated paper obtained by coating both sides of a paper with a resin.

(7) The ink jet recording sheet according to (6), wherein the resin is a polyolefin resin.

(8) The inkjet recording sheet according to (7), wherein the polyolefin resin is a polyethylene resin.

(9) The ink jet recording sheet according to (5), wherein the hydrophobic substrate is a polyester resin film.

(10) The ink jet recording sheet according to (9), wherein the polyester resin film is a polyethylene terephthalate film.

(11) Any one of (1) to (10), wherein at least one of the ink receiving layers contains two or more compounds represented by the general formula [I]. Item 7. The ink jet recording sheet according to Item 1.

(12) The compound according to any one of (1) to (11), wherein the compound represented by the general formula [I] is localized on the side near the support in the ink receiving layer. 3. The ink jet recording sheet according to claim 1.

(13) In the ink receiving layer,
(1) to (12), wherein 80% of the compound represented by the general formula [I] is localized in a portion within a thickness of 50% or less in the ink receiving layer from a portion close to the support. 5. The sheet for inkjet recording according to any one of 1) to 3).

(14) The ink receiving layer has a multilayer structure of two or more layers, and the compound represented by the general formula [I] is added to the lowermost layer.
The inkjet recording sheet according to any one of (13) and (13).

(15) A recording method for recording on an ink jet recording sheet by a color ink jet recording method, wherein the ink jet recording sheet has at least one ink receiving layer on one side of a support, and A recording method, wherein at least one of the receiving layers has a constitution containing at least one kind of the compound represented by the general formula [I]. Hereinafter, the present invention will be described in detail.

The compound used in the present invention has the general formula [I]
It is represented by

[0027]

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As mentioned above, in the formula, Q ¹ and Q ² each represent an acidic nucleus and a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic group, and L ¹ , L ² and L ³ each represent a substituent. Or an unsubstituted methine group; M ⁺ represents a cation;
And n represents a number necessary to offset the charge in the molecule.

In the general formula [I], Q ² is a structural isomer in which the keto structure of the heterocyclic ring represented by Q ¹ is enolized, and the nitrogen-containing heterocyclic group of the acidic nucleus formed by Q ¹ is ,
For example, the following are mentioned.

[0030]

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[0031]

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R ¹ and R ² each represent a hydrogen atom, an alkyl group,
Aryl group, a heterocyclic group, a carbamoyl group, an amino group, a hydroxyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an acyl group, a sulfamoyl group, an alkoxy group, or an aryloxy group, R ^a And R ^b each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, or a sulfonyl group.

Examples of the alkyl group represented by R ¹ and R ² or R ^a and R ^b include a chain group such as methyl, ethyl, propyl and isobutyl, and a cyclic group such as cyclopropyl, cyclopentyl and cyclohexyl. No.
These groups may have a substituent at any position. Specific examples include groups such as 2-sulfoethyl, 3-sulfobutyl, benzyl, allyl, o-sulfobenzyl, p-carboxybenzyl, carboxymethyl, ethoxycarbonylmethyl, trifluoroethyl and trifluoromethyl.

The allyl groups represented by R ¹ and R ² or R ^a and R ^b include, for example, groups such as phenyl and naphthyl, and the heterocyclic groups include pyridyl, thienyl, sulfolanyl, indolyl, indazolyl and piperidyl. , Pyrrole, pyrazyl, thiazolyl and the like, and these groups may have a substituent at any position. Specifically, 4-sulfophenyl, 2,5-disulfophenyl, 4-cyanophenyl, 4-carboxyphenyl,
-Sulfamoylphenyl, 2,5-bis (N, N-dimethylsulfamoyl) phenyl, 4-butanesulfonamidophenyl, 4-chloro-2-pyridyl, 1-methyl-2-imidazolyl, 5-methyl- And groups such as 2-furyl.

The acyl groups represented by R ¹ and R ² or R ^a and R ^b include, for example, groups such as acetyl, benzoyl and propionyl. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, morpholinocarbonyl, piperazinocarbonyl, N, N-dimethylcarbamoyl, and N-propylcarbamoyl.

The amino groups represented by R ¹ and R ² include
Including those having a substituent, for example, amino, N-methylamino, N, N-diethylamino, N-benzylamino, N-acetylamino, N-benzoylamino, N-
Examples include groups such as propionylamino, N-2-pyridylamino, imino-methanesulfonylamino succinate, ethanesulfonylamino, and butaneethanesulfonylamino. Examples of the alkyloxycarbonyl group include groups such as methoxycarbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, and 2,2,2-trifluoroethoxycarbonyl. For example, phenoxycarbonyl, p-methoxycarbonyl and the like.

Examples of the sulfamoyl group include sulfamoyl, N, N-dimethylsulfamoyl, N-benzylsulfamoyl, N, N- (3-oxapentamethylene) sulfamoyl, N, N-pentamethylenesulfamoyl and the like. And the alkoxy group includes
For example, each group such as methoxy, ethoxy, butoxy, 2-methoxyethoxy, 2-hydroxyethoxy, 2-phenoxyethoxy, 2-hydroxypropoxy, 2 (2-hydroxyethoxy) ethoxy, 2-cyanoethoxy, and 2-chloroethoxy Examples of the aryloxy group include phenoxy, 2-naphthoxy, 1-naphthoxy, p-naphthoxy, p-carboxynaphthoxy, p-sulfamoylphenoxy, p-carbamoylphenoxy and the like.

Examples of the sulfonyl group represented by R ^a and R ^b include methanesulfonyl, ethanesulfonyl, butanesulfonyl, p-toluenesulfonyl, benzenesulfonyl and the like.

Examples of the cation represented by M ⁺ include a hydrogen ion, an alkali metal ion such as lithium ion and potassium ion, an ammonium ion, an alkaline earth metal ion such as calcium and magnesium, a triethanolammonium ion and a triethylammonium ion. And other organic ammonium ions.

The methine groups represented by L ¹ , L ² and L ³ may be substituted. Specific examples of the substituent include:
Examples include groups such as methyl, ethyl, phenyl, and benzyl.

In the above general formula (I), the preferred nitrogen-containing heterocyclic group of the acidic nucleus formed by Q ¹ and Q ² is 5
A pyrazolone ring group, a 2,6-pyridinedione ring group, 3,
There are a 5-pyrazolidion ring group, a 2,4,6-pyridinetrione ring group and a 2-thio-2,4,6-pyrimidinetrione ring group, for example, in the following general formulas [Ia] to [Ie]. Some are represented.

[0042]

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In the general formulas [Ia] to [Ie], R ¹¹ and R ¹² are R ¹ and R ² defined in the general formula [I], and R ^a ′ and R ^b ′ Is R ^a and R ^b , and M ¹¹ is M
Are synonymous with each other.

More specifically, the following are given as examples.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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The compounds of the present invention represented by the above general formula [I] are described, for example, in US Pat. No. 3,575,704, JP-A-48-85130, JP-A-49-99620, and JP-A-59-99620.
Nos. 11164 and 59-170838, JP-A-1-1-1
No. 34447, No. 1-183652, No. 4-4633
The compound can be synthesized by the method described in each publication of No. 6 or according to it.

The compound of the present invention contains 0.0
It is preferable to add in the range of 1 to 10 mg / m ² ,
The range is more preferably from 0.03 to 8.0 mg / m ² , and particularly preferably from 0.1 to 4.0 mg / m ² . Also,
More preferably, two or more of the compounds of the present invention represented by the general formula [I] are used in combination.

In addition to the above-mentioned problems, the problem that the color tone changes due to exposure to light in a low-density image is a problem that the method of adding the compound represented by the general formula [I] of the present invention is locally applied to the ink receiving layer. It was found that localization could improve the situation. Specifically, the compound represented by the general formula [I] is preferably localized in the ink receiving layer on the side near the support. 80% of the total weight of the compound represented by the general formula [I] used in the ink receiving layer is localized in a portion within a thickness of 50% or less in the ink receiving layer from a portion close to the support. It is particularly preferable that 80% of the total weight of the compound used in the ink receiving layer is localized in a portion close to the support and within a thickness of 30% or less in the ink receiving layer. When a multilayer coating is applied, it is preferably added to a layer other than the uppermost layer, and more preferably added to the lowermost layer.

In the present invention, a water-soluble polymer is preferably contained as a binder used in the ink receiving layer, and gelatin is preferably used as the water-soluble polymer. The water-soluble polymer in the present invention is a polymer compound derived from natural, synthetic and natural products and is water-soluble. As the gelatin, any gelatin can be used as long as it is made of animal collagen, but gelatin obtained from collagen made of pork skin, cowhide, or bovine bone is preferred. There is no particular limitation on the type of gelatin, but lime-treated gelatin, acid-treated gelatin, and derivative gelatin (for example, Japanese Patent Publication Nos. 38-4854, 39-5514, and 40-12)
Nos. 237 and 42-26345, U.S. Pat.
5,753, 2,594,293, 2,61
Nos. 4,928, 2,763,639, 3,11
8,766, 3,132,945, 3,18
6,846 and 3,312,553, British Patent 86
1,414, 103,189, etc.) can be used alone or in combination.

The derivative gelatin referred to in the present invention means a gelatin substituted with an amino group, an imino group or a carboxyl group of the gelatin. In the present invention, a gelatin substituted with an amino group or an imino group is particularly preferred. More preferably, the amino group-substituted gelatin is used, and examples thereof include phenylcarbamoyl gelatin and phthalated gelatin.

In the present invention, as the derivative gelatin obtained by substituting an amino group, for example, US Pat.
Nos. 91,582, 2,614,928, 2,52
5,753, etc.

In the present invention, useful substituents for obtaining a derivative gelatin by substituting an amino group include (a)
Alkylacyl, arylacyl, acetyl and substitution,
Acyl groups such as unsubstituted benzoyl, (b) sulfonyl groups such as alkylsulfonyl and arylsulfonyl, (c)
Carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl; (d) thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl; (e) linear and branched alkyl groups having 1 to 18 carbon atoms; (f) substituted and unsubstituted And aryl groups such as aromatic heterocycles such as phenyl, naphthyl and pyridyl and furyl.

The derivative gelatin of the present invention is preferably a gelatin in which an amino group is substituted by an acyl group (—COR ¹ ) or a carbamoyl group (—CONR ¹ R ² ).

R ¹ of the acyl group or the carbamoyl group is a substituted or unsubstituted aliphatic group (eg, an alkyl group having 1 to 18 carbon atoms, an allyl group), an aryl group or an aralkyl group (eg, a phenethyl group). And R ² is a hydrogen atom, an aliphatic group, an aryl group or an aralkyl group.

Particularly preferred in the present invention are R ¹
Is an aryl group, and R ² is a hydrogen atom. Hereinafter, examples of the substituent of the amino group of the derivative gelatin used in the present invention are shown, but the present invention is not limited thereto.

-Examples of amino group substituents of derivative gelatin-

[0107]

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The derivative gelatin in the present invention is a substituted gelatin in which 60% or more of the total amount of at least one selected from amino groups and imino groups can react with the amino groups or imino groups in order to quickly absorb the ink into the receptor layer. It is preferable to use those which have been previously substituted with a group, but particularly preferred is a derivative gelatin in which 80% or more of the total amount of amino groups is substituted.

The gelatin of the present invention has a jelly strength (PAGI method, bloom type jelly strength meter) of 15%.
0 g or more, preferably 200 to 300 g.

Examples of preferably used water-soluble polymers other than gelatin include polyvinyl alcohols,
Vinyl formal such as polyvinyl pyrrolidone and various modified polyvinyl alcohols and derivatives thereof
No. 145879, No. 60-220750, No. 61-1
No. 43177, No. 61-235182, No. 61-23
Nos. 5183, 61-237681, 61-261
No. 089), polymers containing an acrylic group such as polyacrylamide, polydimethylacrylamide, polydimethylaminoacrylate, and vinyl alcohol acrylate copolymer salts (JP-A-60-168651, JP-A-62-9).
988), starch, oxidized starch, carboxyl starch,
Natural polymers such as dialdehyde starch, cationized starch, dextrin, gum arabic, casein, pullulan, dextran, methylcellulose, ethylcellulose, carboxymethylcellulose, and hydroxypropylcellulose or derivatives thereof (Japanese Patent Application Laid-Open Nos. 59-174382, 6).
Nos. 0-262885, 61-143177, 61
181679, 61-193879, 61-
No. 287782), polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyvinyl ether, polyglycerin, maleic acid alkyl vinyl ether copolymer, maleic acid N-vinylpyrrole copolymer, styrene maleic anhydride copolymer, polyethylene Synthetic polymers such as imine
No. 32787, No. 61-237680, No. 61-2
77483) and the like.

In the present invention, it is preferable to use two or more water-soluble polymers in combination. It is preferable to use gelatin and one or more water-soluble polymers other than the above-mentioned gelatin in combination, and it is more preferable to use gelatin and two or more water-soluble polymers in combination.

Among these, particularly preferred are polyvinylpyrrolidones, polyvinyl alcohols, and polyalkylene glycols. The proportion of these water-soluble polymers in the ink receiving layer is preferably from 10 to 70 wt%, more preferably from 20 to 60 wt%.

The ink receiving layer according to the present invention has a glass transition temperature of 60 ° C. for the purpose of improving the glossiness of the printed portion.
The above anionic urethane polymers can be used.

The anionic urethane polymer according to the present invention is an addition polymer of a polyisocyanate compound and a polyol having two or more hydroxyl groups, and is a urethane polymer having an anionic group at a side chain or at a terminal.

The urethane polymer used in the present invention is preferably an aqueous dispersion which does not require the use of an organic solvent during coating from the viewpoint of environmental problems. There are two types of urethane polymer aqueous dispersions: a "forced emulsification type" which emulsifies by using an external surfactant and a "self-emulsifying type" which emulsifies after introducing hydrophilicity into the urethane polymer skeleton. In the present invention, any type can be used, but it is preferable that the ink jet recording sheet is “self-emulsifying type” in terms of gloss and transparency.

The polyisocyanates useful for forming the polyurethane include those having two isocyanate groups, such as 1,2-diisocyanateethane, 1,3-diisocyanatepropane, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and nona Methylene diisocyanate, decamethylene diisocyanate, ω, ω'-dipropyl ether diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-
Diisocyanate, hexahydrodiphenyl-4,4 '
-Diisocyanate, hexahydrodiphenyl ether-4,4'-diisocyanate, phenylene-1,4-
Diisocyanate, toluylene-2,6-diisocyanate, toluylene-2,4-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-chlorophenylene diisocyanate, tetrachlorophenylene diisocyanate, meta-xylylene diisocyanate, para-xylylene diisocyanate, Diphenylmethane-4,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylether-
4,4'-diisocyanate, diphenyl ether-
3,4'-diisocyanate, diphenyl ketone-4,
4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate,
2,4'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, 3,3'-dimethoxy-
4,4'-biphenyl diisocyanate, anthraquinone-2,6-diisocyanate, triphenylmethane
4,4'-diisocyanate, azobenzene-4,4 '
-Diisocyanate and the like.

As the compound containing three isocyanate groups, for example, compounds represented by the following structural formulas (I) to (IV) can be used.

[0118]

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Suitable polyols having two or more hydroxyl groups include diols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, trimethylolethane, trimethylolpropane, hexanetriol and glycerin. Triols, hexaols such as sorbitol, polyester polyols, polyether polyols, and polyester polyether polyols.Polyester polyols are compounds produced from polybasic acids and polyhydroxy compounds, and terminal hydroxy polyesters are preferred. It is. As polybasic acids, oxalic acid,
Saturated fatty acids such as succinic acid, adipic acid and pimelic acid, unsaturated fatty acids such as maleic acid and fumaric acid, phthalic acid,
An aromatic acid such as isophthalic acid or an anhydride thereof is used alone or as a mixture, and as a polyhydroxy compound, diols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol, trimethylolpropane, trimethylolethane, hexanetriol, glycerin, etc. Or one or more of hexaols such as triol and sorbitol.

The polyether polyol used in the present invention is a compound containing two or more hydroxyl groups in one molecule and having an ether bond, and is a homopolymer of ethylene oxide (EO) and propylene oxide (PO). Or a copolymer, a polyhydric alcohol such as glycerin, trimethylolpropane, triol such as hexanetriol, hexaol such as sorbitol or ethylenediamine, benzenesulfamide, 2-aminoethanolamine, N-methyldiethanolamine, diethylenetriamine, or aromatic. Amines such as amines having a group
A polyol formed by optionally adding O or PO,
Or derivatives thereof, and one or two of these
More than one species can be mixed and used. The polyester polyether polyol is obtained by condensing the above polybasic acid and polyether polyol so as to be a terminal hydroxyl group.

Other polyols include, for example, castor oil, tall oil or derivatives thereof, acryl polyol, urethane polyol and the like. Further, the above-mentioned various polyols can be used alone or as a mixture.

The preparation of the polyurethane comprising the above components can be carried out by any known method.

The glass transition temperature of the urethane polymer of the present invention is 60 ° C. or higher, preferably 70 ° C. or higher.

The glass transition temperature can be measured by a known method utilizing the fact that the coefficient of thermal expansion, specific heat, and the like change discontinuously in the process of changing the temperature.

As the anionic urethane polymer that can be used in the present invention, a “self-emulsifying type” in which an anionic group is introduced into a urethane polymer skeleton and then emulsified, is preferable.

Representative examples of the above anionic group include:
A carboxyl group, a sulfonic group, a sulfate group, a phosphate group and the like.

For the purpose of preventing adhesion failure such as blocking, a matting agent is used in an amount of about 0.005 to 0.1 g / m ² ,
It can be contained in the front and / or back layers.

Matting agents are well known in the photographic art and can be defined as discrete solid particles of an inorganic or organic material dispersible in a hydrophilic organic colloid binder. Examples of inorganic matting agents include oxides (eg, silicon dioxide, titanium oxide, magnesium oxide, aluminum oxide, etc.) and alkaline earth metal salts (eg, sulfates and carbonates, specifically, barium sulfate, carbonate Calcium, magnesium sulfate, calcium carbonate, etc., silver halide grains which do not form an image (silver chloride, silver bromide, etc., to which iodine atom may be added as a halogen component even a little), glass and the like.

In addition, West German Patent 2,529,321
Nos., British Patent Nos. 760,775 and 1,260,77
No. 2, U.S. Pat. Nos. 1,201,905 and 2,19
No. 2,241, No. 3,053,661, No. 3,06
2,649, 3,257,206, 3,32
2,555, 3,353,958, 3,37
No. 0,951, 3,411,907, 3,43
7,484, 3,523,022 and 3,61
5,554, 3,635,714, 3,76
9,020, 4,021,245, 4,02
No. 9,504 and the like can also be used.

Examples of the organic matting agent include starch, cellulose ester (eg, cellulose acetate propionate, etc.), cellulose ether (eg, ethyl cellulose, etc.), and synthetic resin. Examples of synthetic resins are water-insoluble or poorly soluble synthetic polymers such as alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate,
(Meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin (for example, ethylene, etc.), styrene, benzoguanamine formaldehyde condensate alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid A polymer having a combination of hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid, or the like as a polymer component can be used.

Other epoxy resin, nylon, polycarbonate, phenol resin, polyvinyl carbazole,
Polyvinylidene chloride can also be used.

In addition, British Patent No. 1,055,713
No. 1,933,213 and 2,221,
873, 2,268,662, 2,322,0
Nos. 37, 2,376,005 and 2,391,18
No. 1, 2,701,245, 2,992,101
No. 3,079,257 and 3,262,782
No. 3,443,946, No. 3,516,832
Nos. 3,539,344 and 3,591,379
Nos. 3,754,924 and 3,767,448
And JP-A-49-106821 and 57-14835.
Organic matting agents described in Nos. 1 and 2 can be used.

Above all, polymethyl methacrylate, benzoguanamine formaldehyde condensation polymer (benzoguanamine resin, specifically represented by the following formula, for example, trade name: eposter: Nippon Shokubai Chemical Co., Ltd .: existing chemical substances 7-31, etc.) , Polyolefin (for example, trade name: Flowbeads LE-1080, CL-2080, HE-5
023: Made by Iron and Steel Chemical or trade name Chemipearl V-10
0: manufactured by Mitsui Petrochemical)

[0134]

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Preferred are polystyrene beads (manufactured by Moritex), nylon beads (manufactured by Moritex), AS resin beads (manufactured by Moritex), epoxy resin beads (manufactured by Moritex), polycarbonate resins (manufactured by Moritex), and the like.

These matting agents may be used in combination.

In the present invention, a surfactant may be added to the ink receiving layer in order to improve dot reproducibility in addition to the binder. The surfactant used may be any of anionic, cationic, nonionic and betaine types, and may be of low molecular weight or high molecular weight. The addition amount of the surfactant is preferably 0.001 g to 5 g, more preferably 0.01 to 3 g, per 100 g of the binder constituting the ink receiving layer.

In the present invention, it is preferable that a fluorine-based surfactant is contained in the ink-receiving layer, and when the ink-receiving layer is composed of two or more layers, it is preferable that the fluorine-containing surfactant is contained in the uppermost layer. As the fluorine-based surfactant, an anionic and / or cationic one is preferable.

As the anionic fluorinated surfactant preferably used in the present invention, those represented by the following general formula (FA) can be mentioned.

Formula (FA) (Cf)-(Y) _{n In the} formula, Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is —COO
_{M, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ . M is a hydrogen atom or an alkali metal or quaternary
Represents a cation such as a quaternary ammonium salt, wherein n is 1 or 2
It is.

The anionic fluorine-based surfactants more preferably used are those represented by the following formula (FA ').

[0142] In Formula (FA ') Rf- (D) t -Y formula, Rf is an aryl group having a fluorine-substituted alkyl group or a carbon atom number of 3 to 30 concentrations of fluorine-substituted alkyl group having 3 to 30 carbon atoms And D represents -O-, -COO-,
-CON (R ₁₎ - or -SO ₂ N (R ₁₎ - represents a composed combine at least one divalent group having 1 to 12 carbon atoms. R ₁ represents an alkyl group having 1 to 5 carbon atoms, t is 0, 1 or 2, Y is -COOM, -SO ₃ M, -
OSO ₃ represents M or -P (= O) (OM) 2, M + represents such cation hydrogen atom ion or an alkali metal or a quaternary ammonium ion.

Next, specific examples of the compound represented by formula (FA) will be shown, but the present invention is not limited thereto.

[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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It is particularly preferable to use an anionic fluorinated surfactant containing at least one bond of —SO ₂ N (R ₁ ) —.

The cationic fluorine-based surfactant preferably used in the present invention is a compound represented by the following formula (FK).

[0151] Formula (FK) Rf'-L-X + Z - wherein, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen atom is substituted with a fluorine atom. L represents a chemical bond or a divalent group. X ⁺ is a cation, Z ^- represents a counter anion.

Examples of [0152] Rf _{'are, -C m F 2m + 1,} -C m
F _2m-1 (m = 2 to 20, particularly preferably 3 to 12) and the like.

Examples of L include —SO ₂ N (R ₁ ) (CH
_{2) p -, - CON (} R 1) (CH 2) p -, - OArSO 2
_{N (R 1) (CH 2} ) p -, - OArCON (R 1) (CH
_{2) p -, - OArO (} CH 2) p -, - OAr (CH 2) p
_{-, - O (CH 2 CH} 2 O) q (CH 2) p -, - O (C
_{H 2) p -, - N} (R 1) (CH 2) p -, - SO 2 N
(R ₁ ) (CH ₂ ) _p O (CH ₂ ) _r- , -CON (R ₁ )
_{(CH 2) p O (CH} 2) r -, - OArSO 2 N (R 1)
_{(CHR 1) p OAr -,} - (CH 2) p (CHOH)
_s (CH _{2) r} -, and the like can be given. Here, Ar represents an aryl group.

Examples of X ⁺ include -N ⁺ (R ₁ ) ₃ , -N ⁺
_{(CH 2 CH 2 OCH 3)} 3, -N + C 4 H 8 O (R 1), - N
_{^{+ (R 1) (R 2}} ) (CH 2 CH 2 OCH 3), - N + C
^{_{5 H 5, -N + (R}} 1) (R 2) (CH 2) p C 6 H 5, -N
⁺ (R ₁ ) (R ₂ ) (R ₂ ) and the like. Here, R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may have a substituent);
s is each 0-6, and q is 1-20.

[0155] Z ^- Examples ^{of, I -, Cl -, Br} -, C
H ₃ SO ₃ ⁻ , CH ₃ —C ₆ H ₄ —SO ₃ ^{— and the} like can be mentioned.

Specific examples of the cationic fluorine-based surfactant preferably used in the present invention are shown below, but are not limited thereto.

[0157]

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[0158]

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The anionic fluorinated surfactants or cationic fluorinated surfactants according to the present invention include, for example, US Pat. Nos. 2,559,751 and 2,567,011,
2,732,398, 2,764,602, 2,806,866, 2,809,998, 2,915,376, 2,915,528, and 2 918,501, 2,934,450, 2,937,098, 2,957,031, 3,472,894, 3,555,089, British Patent 1, No. 143,927, No. 1,130,822,
JP-B-45-37304, JP-A-47-9613,
Nos. 49-134614, 50-117705, 50-117727, 50-112243, and 5
2-41182, 51-12392, British Chemical Society (J. Chem. Soc.), 1950, p. 2789,
1957, pp. 2574 and 2640, Journal of the American Chemical Society (J. Amer. Chem. Soc.) 79, 2549.
(1957), Oil Chemistry (J. Japan Oil)
Chemists Soc. ), P. 653, J. Org. Chem., Vol. 30, p. 3524 (1965), and the like.

[0160] Among these fluorine-based surfactants, a certain one is a trade name of Megafac F from Dainippon Ink and Chemicals, and Fluorad (trade name) from Minnesota Mining and Manufacturing Company. Fluorad) under the trade name of FC, Imperial Chemical Industries under the trade name of Monflor, E.I.Dupont Nemelas and Company under the trade name of Zonyls, and Farbeberke. Licovet V from Hoechst
Each is marketed under the trade name PF.

In the present invention, the effects of the present invention can be more favorably achieved by using at least one of the anionic fluorine-based surfactant and the cationic fluorine-based surfactant.

The total amount of the cationic fluorosurfactant and the anionic fluorosurfactant preferably used in the present invention is preferably 0.1 to 1000 mg per 1 m ² ,
Preferably 0.5-300 mg, more preferably 1.0
~ 150 mg is good. When used in combination, two or more of them may be used in combination. In addition, a nonionic fluorine-based surfactant, a betaine-type fluorine-based surfactant, or a hydrocarbon-based surfactant may be used in combination.

The molar ratio of the anionic fluorine-based surfactant to the cationic fluorine-based surfactant was 1:10.
The ratio is preferably from 10 to 10: 1, and more preferably from 3: 7 to 7: 3.

In the present invention, the ink receiving layer can be hardened with an appropriate hardener for the purpose of improving water resistance and dot reproducibility. Specific examples of the hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, and bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1. 3,3,5 triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, US Pat. N-methylol compounds as described in Japanese Patent No. 2,732,316, U.S. Pat. No. 3,103,43
No. 7, isocyanates described in US Pat.
Aziridine compounds as described in US Pat. Nos. 7,280 and 2,983,611; carbodiimide-based compounds as described in US Pat. No. 3,100,704;
No. 91,537, epoxy compounds, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum,
There are inorganic hardeners such as potassium alum and zirconium sulfate, and these can be used alone or in combination of two or more. Preferred are triazine-based, divinylsulfone-based, and epoxy-based hardeners. The amount of the hardener added was 0.0 to 100 g of gelatin constituting the ink receiving layer.
The amount is preferably 1 to 10 g, and more preferably 0.1 to 5 g.

In the present invention, the ink-receiving layer further contains, in addition to the above-mentioned surfactant and hardener, an inorganic pigment, a coloring dye, a coloring pigment, a fixing agent for the ink dye, an ultraviolet absorber, an antioxidant, and a pigment. Various known additives such as a dispersant, an antifoaming agent, a leveling agent, a preservative, an optical brightener, a viscosity stabilizer, and a pH adjuster can also be added.

The ink jet recording sheet used in the present invention can be obtained by providing an ink receiving layer on a hydrophobic base material such as a transparent or opaque film or resin-coated paper, whose surface does not have water absorption. Preferred ones are obtained in terms of water resistance and texture of the image. The thickness of the ink receiving layer in the present invention is preferably 0.5 to 100 μm,
Particularly preferably, it is 1 to 70 μm, more preferably 3 to 3 μm.
0 μm. As the substrate to be used, any of conventionally known substrates can be used. For example, as a transparent substrate, polyester resin, diacetate resin, triacetate resin,
Examples include films or plates such as acrylic resins, polycarbonate resins, polyvinyl chloride, polyimide resins, cellophane, and celluloid, and glass plates.

Such a transparent substrate has a thickness of 10 to 1
It is preferably about 000 μm. It is more preferably from 30 to 300 μm, particularly preferably from 50 to 300 μm.
250 μm. As the opaque substrate, synthetic paper, resin-coated paper, opaque film containing pigment, foamed film and the like can be used.

Particularly preferred is a resin-coated paper having both sides coated with a resin similar to a polyester resin such as polyethylene terephthalate or a support for photographic printing paper. An ink receiving layer is provided on the surface of such a substrate. Is the most preferred embodiment of the present invention.

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 base paper used for a photographic support is used. preferable. 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. The base paper is blended with additives generally used in papermaking, such as a sizing agent, a paper strength enhancer, a filler, an antistatic agent, a fluorescent whitening agent, and a dye.

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 applied to the surface.

The thickness of the base paper is not particularly limited, but preferably has good surface smoothness, such as by applying pressure by using a calender or the like during or after paper making, and the basis weight is 30 to 30%. 250 g / 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.
Examples of the polyolefin resin include 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. Various densities,
Those having a melt viscosity index (melt index) can be used alone or as a mixture thereof.

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.

In the case of polyolefin resin on a running base paper, the resin-coated paper which is preferably used in the present invention is produced by a so-called extrusion coating method in which a heat-melted resin is cast. 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 activation treatment such as corona discharge treatment and flame treatment as required. The thickness of the coating resin layer is not particularly limited, but it is generally coated on the surface or on both the front and back to a thickness of 5 to 50 μm.

In the present invention, various types of back coat layers can be applied to the substrate 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.

The aqueous ink referred to in the present invention is a recording liquid comprising the following colorant, liquid medium and other additives. Examples of the coloring agent include a direct dye, an acid dye, a basic dye, a reactive dye, and a water-soluble dye such as a food colorant.

As the solvent for the aqueous ink, water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, C1-C4 alkyl alcohols such as isobutyl alcohol; amides such as dimethylformamide and dimethylacetamide;
Ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,2 6-hexanetriol, thiodiglycol, hexylene glycol,
Alkylene glycols having 2 to 6 alkylene groups such as diethylene glycol; lower alkyl ethers of polyhydric alcohols such as glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol and monomethyl ether; 2H-pyrrolidinone And pyrrolidones such as 1-methyl-2-pyrrolidone and 2-pyrrolidone. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and pyrrolidones are preferable.

In the present invention, a mixed solvent of water and the above organic solvent is preferably used as a solvent for the ink from the viewpoint of preventing clogging of the ink head nozzle.
The mixing ratio of water and the organic solvent is 30/70 / -70 by weight.
/ 30 is preferable, and more preferably 40/60 to 70 /
30.

Other additives include, for example, a pH adjuster, a metal sequestering agent, a fungicide, a viscosity adjuster, a surface tension adjuster, a wetting agent, a surfactant, and a chain inhibitor.

As the method for forming the ink receiving layer of the present invention, when a coating layer is formed on a substrate, a size press method, a roll coater method, a blade coater method, an air knife coater method, a gate roll coater method, A commonly used coating method such as a rod bar coater method, a curtain method, and an extrusion method is used. Further, as described above, the ink receiving layer can be provided in the base material by the internal addition method in which the material constituting the ink receiving layer is mixed with the pulp slurry to form a paper.

The drying method after coating is not particularly limited, but the cold drying method described on page 4 of JP-A-6-64306 is a preferable drying method for obtaining a high-quality recording sheet. is there.

[0182]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the description, “parts” means “parts by weight” unless otherwise specified.

Example 1 A commercially available high-quality paper (basis weight: 80 g / m ² ) was coated with an ink receiving layer coating solution having the following composition by a bar coating method so that the film thickness after drying was about 10 μm. A sheet sample was prepared.

Lime-treated gelatin (KV-3000 manufactured by Konica Gelatin Co., Ltd.) 98.2 parts by weight Exemplified compound (types and amounts of compounds described in Table 1) Surfactant FA 0.15 parts by weight Surfactant FK 0.15 Parts by weight Surfactant FT 0.5 parts by weight Organic matting agent 1 part by weight * Solid content concentration of coating liquid: 8 wt / vol% * Coating liquid pH: adjusted to pH 7.5 using 5 wt / vol% NaOH aqueous solution. Was.

[0185]

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Next, the obtained sample was stored for one month in an environment of 35 ° C. and 80% RH, and the perceived chromaticity index b * by CIELAB of the surface of the ink receiving layer before and after the storage was Gretag.
The value obtained by subtracting the value after preservation from the value before preservation and measuring with a color difference meter SPM50 manufactured by Co., Ltd. was defined as Δb *, and the result of visual evaluation is shown in Table 1.

Evaluation criteria A: Less than 0.1, no change in color tone is visible B: From 0.10 to less than 0.15, slight change in color tone is slightly visible, but no practical problem at all C: 0.15 or more and less than 0.20, the change in color tone is slightly yellowish, but there is no practical problem D: 0.20 or more and less than 0.40, the color tone is also strongly yellowish, A level that poses a problem in practical use E: A level that is 0.40 or more and is not practical at all

[0188]

[Table 1]

As is evident from the results in Table 1, the samples using the compounds of the present invention showed almost no change in color tone even when stored under high humidity and had good storage stability. The color development of the image was also good. On the other hand, when the compound of the present invention was not used, the color tone shifted to the yellow direction during storage under high humidity, the printed image became yellowish, and the color developability was poor.

Example 2 Commercially available polyethylene resin-coated paper (100 g / m ² base paper with polyethylene layer: 25 g / m ² (low density polyethylene: 70 parts, high density polyethylene: 20 parts, titanium oxide: 10 parts) And a polyethylene layer composed of 50 parts of high-density polyethylene and 50 parts of low-density polyethylene on the back surface: 2
5 g / m ² ) A coating solution of the ink receiving layer prepared in Example 1 was applied on a support and a commercially available white polyethylene terephthalate film (thickness: 100 μm) by bar coating so that the film thickness after drying was about 10 μm. A sheet sample for inkjet recording was prepared by applying the same method, and the same evaluation as in Example 1 was performed.

As a result, the storage stability of the sample using the compound of the present invention was excellent, as in Example 1, and in addition to the fact that no wrinkles were generated by the ink in the print area, the sample was smooth and glossy. A high quality print image was obtained.

Example 3 An ink receiving layer coating solution having the following composition was applied to the polyethylene resin-coated paper used in Example 2 by a bar coating method so that the film thickness after drying was about 10 μm. Was prepared.

Lime-processed gelatin (KV-3000, manufactured by Konica Gelatin Co., Ltd.) 50.0 parts by weight Polyethylene glycol cerazole 100A (manufactured by Meisei Chemical Co., Ltd.) 48.7 parts by weight Exemplary compound a-4 0.025 parts by weight Surfactant FA 0 .15 parts by weight Surfactant FK 0.15 parts by weight Surfactant FT 0.5 parts by weight Organic matting agent 1 part by weight * Solid content concentration of coating liquid: 8 wt / vol% * Coating liquid pH: 5 wt / vol% The pH was adjusted to 7.5 using an aqueous NaOH solution.

The above samples were evaluated for storage stability in the same manner as in Example 1. As a result, good results were obtained as in Example 1. Also, inkjet printer: BJC-600J
A solid image of B, G, and R was printed by (manufactured by Canon Inc.), and the image quality was visually checked.
The unevenness in density was remarkably reduced as compared with the sample prepared in the above, and a uniform image was obtained.

Example 4 The following coating was performed on a polyethylene terephthalate film.

First layer (bottom layer) Lime-treated gelatin (KV-3000 manufactured by Konica Gelatin) 1.2 g / m ² Polyvinylpyrrolidone K-90 (manufactured by BASF) 0.8 g / m ² Exemplary compound (Type of compound And the amount added are shown in Table 2) Second layer Lime-treated gelatin (KV-3000 manufactured by Konica Gelatin) 5.0 g / m ² Polyvinylpyrrolidone K-90 (manufactured by BASF) 3.0 g / m ² Polyurethane F-8438D ( 2.0 g / m ² polyethylene glycol 20000 (manufactured by Merck) 1.0 g / m ² Third layer (top layer) Lime-treated gelatin (KV-3000 manufactured by Konica Gelatin) 0.5 g / m m ² polyvinylpyrrolidone K-90 (manufactured by BASF) 0.4 g / m ² polyurethane F-8438D (manufactured by Daiichi Kogyo Yakuhin) 0.4 g / m ² polyethylene Gris Lumpur 20000 (Merck) 0.2 g / m ² Surfactant FA 3 mg / m ² Surfactant FK 3 mg / m ² Surfactant FT 20 mg / ^{m 2} Matting agent 60 mg / m ² then the resulting sample In an environment of 35 ° C. and 80% RH
CIELA on the surface of the ink receiving layer before and after storage
The perceived chromaticity index b * according to B was determined by Gret as in Example 1.
The value obtained by subtracting the value after storage from the value before storage and measuring with a color difference meter SPM50 manufactured by Ag Co., Ltd. was defined as Δb *, and the result of visual evaluation is shown in Table 2. The evaluation criteria were the same as in Example 1.

[0197]

[Table 2]

As is evident from the results in Table 2, the use of the two compounds of the present invention caused almost no change in color tone even under storage under high humidity, and the storage stability was good, compared with the use of the compounds alone. The color development of the print image using the sample was further excellent.

Example 5 A coating solution having the following composition was applied to the polyethylene resin-coated paper used in Example 2 by a slide hopper method, and a sample 5-1 was prepared.
~ 5-5 were produced.

In the samples 5-1 to 5-5, the ink receiving layer was divided into three layers, and all the layers were coated simultaneously. In Table 3 below, the first layer, the second layer, the third layer
Layer (top layer).

Composition of Coating Liquid Lime-treated gelatin (KV-3000 manufactured by Konica Gelatin) 5.0 g / m ² Polyvinylpyrrolidone K-90 (manufactured by BASF) 2.0 g / m ² Modified PVA (Ecomati AX Nippon Synthetic Chemical Industry Co., Ltd.) Graft of polyoxyalkylene onto polyvinyl alcohol / allyl alcohol copolymer 3.0 g / m ² surfactant Exemplified compound FA-19 Table 3 (g / m ² ) Surfactant Exemplified compound FK- 21 Table 3 (g / m ² ) Exemplified compound a-16 of the general formula [A] Table 3 (g / m ² ) The concentration of the coating solution was adjusted to 80 g / L with ion-exchanged water. The pH of the coating solution was adjusted to 7.5 using an aqueous sodium hydroxide solution.

The following evaluation was performed for each sample.

Color Change under High Temperature and High Humidity Environment The characteristics under a 35 ° C., 80% RH environment were examined in the same manner as in Example 1.

Degradation of Color Tone by Light in Low Density Area White and gray lattice patch images were printed in a color mode of a color inkjet printer MJ-810C (manufactured by Seiko Epson Corporation) (gray reflection density: about 0.3). Xenon fade meter (illuminance 70,0
(00 lux) for 24 hours, and changes in color tone were visually compared.

The following five-step evaluation was performed.

Evaluation criteria A: very good with little change B: good with some change C: change is recognized but within the practical range D: considerable change in color tone and problematic in practical use E: change in color tone Has a significant problem, and the results are shown in Table 3 below.

[0207]

[Table 3]

From the results shown in Table 3, it can be seen that the addition of the compound of the present invention improves the change in color tone in storage stability under high temperature and high humidity conditions, reduces the color tone deterioration in low density areas due to light, and gives good results. It turns out that a result is obtained. Sample 5
The compound of the present invention in the layer below the ink receiving layer
It can be seen that particularly good results are obtained when 0% by weight or more is localized.

[0209]

According to the present invention, firstly, it is possible to provide a glossy and high quality ink jet recording sheet which is excellent in the preservability of the recording sheet. Secondly, it is possible to provide an ink jet recording sheet having an ink receiving layer having excellent image resolution and uniformity.

Claims (15)

[Claims] An ink jet recording sheet having at least one ink receiving layer on one side of a support,
An ink jet recording sheet comprising at least one compound represented by the following general formula [I] in at least one of the ink receiving layers. Embedded image [Wherein, Q ¹ and Q ² each represent an acidic nucleus and a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic group, and L ¹ , L ² and L ³ each represent a substituted or unsubstituted methine group , M represents a cation, m represents an integer of 0 to 4, and n represents a number required to cancel the intramolecular charge. ] 2. The method according to claim 1, wherein the content of the compound represented by the general formula [I] is at least 0.01 in at least one of the ink receiving layers.
The ink jet recording sheet according to claim 1, wherein the range of to 10 mg / m ^2. 3. The ink-jet recording sheet according to claim 1, wherein at least one of the ink receiving layers contains a water-soluble polymer. 4. The ink jet recording sheet according to claim 3, wherein the water-soluble polymer is selected from gelatins, polyvinylpyrrolidones, polyvinyl alcohols, and polyalkylene glycols. 5. The inkjet recording sheet according to claim 1, wherein the support is a hydrophobic substrate. 6. The ink jet recording sheet according to claim 5, wherein the hydrophobic substrate is a resin-coated paper obtained by coating both sides of a paper with a resin. 7. The sheet according to claim 6, wherein the resin is a polyolefin resin. 8. The sheet according to claim 7, wherein the polyolefin resin is a polyethylene resin. 9. The sheet according to claim 5, wherein the hydrophobic substrate is a polyester resin film. 10. The ink jet recording sheet according to claim 9, wherein the polyester resin film is a polyethylene terephthalate film. 11. The ink-receiving layer according to claim 1, wherein at least one of the ink-receiving layers contains two or more compounds represented by the general formula [I]. Sheet for inkjet recording. 12. The ink receiving layer according to claim 1, wherein the compound represented by the general formula [I] is localized on the side near the support in the ink receiving layer.
Item 7. The ink jet recording sheet according to Item 1. 13. In the ink receiving layer, 80% of the compound represented by the general formula [I] is localized from a portion close to the support to a thickness within 50% of the ink receiving layer. The inkjet recording sheet according to any one of claims 1 to 12, wherein: 14. The ink receiving layer according to claim 1, wherein the ink receiving layer has a multilayer structure of two or more layers, and the compound represented by the general formula [I] is added to the lowermost layer.
The inkjet recording sheet according to any one of the above items. 15. A recording method for recording on an inkjet recording sheet by a color inkjet recording method,
The ink jet recording sheet has at least one ink receiving layer on one side of the support, and at least one of the ink receiving layers contains at least one compound represented by the above general formula [I]. A recording method, comprising: