JP2003072223A - Material to be ink-jet-recorded - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material to be ink-jet-recorded, the coating layer strength of the ink recording layer of which is high and which is excellent in continuous paper feeding properties in an ink jet recording device in the material to be ink-jet-recorded, which is formed by providing an ink jet receiving layer on a support. SOLUTION: In the material to be ink-jet-recorded, which is formed by providing the ink receiving layer on the support, the ink receiving layer includes a hydrazine derivative and a water-soluble multivalent metal salt. The preferable water-soluble multivalent metal salt is an organic acid metal salt. The preferable support is an acid paper. As a preferable embodiment, a pigment employed in the ink receiving layer is an amorphous silica.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording material, and more particularly, to an ink jet recording material having a high coating strength of an ink receiving layer and excellent continuous feeding property in an ink jet recording apparatus. It is a thing.

[0002]

2. Description of the Related Art An ink jet recording system is a system in which minute droplets of ink are ejected according to various operating principles to adhere to a recording material such as paper to record an image or characters. The inkjet recording device used for inkjet recording is
The flexibility of the recording pattern is great, the high-speed printing property and the low noise property are excellent, and the features such as no development and fixing are required, and not only can complex images be formed accurately and quickly, but especially characters created by a computer and As a hard copy creating apparatus for image information such as various figures, it has become popular rapidly in recent years. It is also easy to perform multicolor recording using a plurality of ink nozzles. The color image formed by the multi-color inkjet recording method can obtain a recording comparable to that of the multi-color printing by the plate making method or the printing by the color photographic method. However, it is being widely applied because it is more economically advantageous than the printing method and the photographic method.

Further, with the diversification of applications, it has come to be used for large format posters, POP arts, and drawing applications. In these applications, the high sharpness of the ink jet is utilized and the excellent color property allows the formation of a good image, which has a great advertising effect. Adaptation to these is also a reason for diversifying inkjet recording materials because it is possible to easily obtain images with excellent image reproducibility and color reproducibility such as sharpness and color at the personal computer level. There is.

With the recent increase in the number of hard copies, such an ink jet recording apparatus is required to have a higher speed. Increasing the speed of ink jet recording apparatuses has been realized by improving ink ejection speed, arranging ink nozzles in parallel and increasing size, improving ink nozzle moving speed, and improving ink absorption speed of ink jet recording material. Due to the increase in the speed of the inkjet recording apparatus, the conveying speed of the inkjet recording material has increased, so that an inkjet recording material having excellent conveying properties corresponding to the increase has been required.

[0005] A characteristic that affects the transportability of such an inkjet recording material is the coating layer strength of the inkjet recording material. In the inkjet recording apparatus, the inkjet recording material is mainly conveyed by a pickup roll-covering elastic body (paper feeding roller). If the coating layer strength of the ink jet recording material is weak, the ink receiving layer peels from the support, and the powder of the ink receiving layer adheres to the paper feed roller when it is conveyed by the ink jet recording apparatus. When the amount of powder in the ink receiving layer adhering to the paper feed roller increases, the coefficient of friction between the inkjet recording material and the paper feed roller decreases, and continuous paper feeding causes paper feed failure and paper discharge failure.

There have been many proposals for increasing the coating strength of the ink receiving layer. The method of overcoating the ink receiving layer with a resin or the like or the method of curing the hydrophilic binder in the ink receiving layer lowers the ink absorbability of the ink receiving layer and causes bleeding at the print boundary. JP-A-5
JP-A-221115 discloses an inkjet recording material in which starch particles are added to an ink receiving layer, but the strength of the ink receiving layer itself is increased, but it is not satisfactory in terms of ink bleeding and transfer to other paper. Is enough. Also,
It is described that these increase the coating strength of the ink receiving layer.

Japanese Unexamined Patent Publication (Kokai) No. 6-278357 discloses a method using colloidal silica. When continuous paper feeding is carried out, the initial carrying property is good, but as the number of carried paper sheets increases, the ink jet ink is used. The coefficient of friction between the recording material and the paper feed roller tends to decrease, resulting in defective paper feeding and defective paper ejection.

JP-A-61-154989 describes that the light resistance is improved by containing a hydrazine compound in the ink receiving layer.

JP-A-59-155089 describes that light resistance is improved by containing a water-soluble metal salt having a valency of 2 or more in the ink receiving layer.

JP-A-1-301359 discloses that the light resistance is improved by containing an organic sulfonate, an organic sulfate sulfonate, and a monocarboxylic acid salt. Describes that light resistance is improved by containing a borohydride salt and p-toluenesulfonate in the ink receiving layer.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an ink jet recording material having a high coating strength of an ink receiving layer and excellent continuous feeding property in an ink jet recording apparatus.

[0012]

The present inventor has conducted extensive studies on a method of increasing the coating layer strength in order to provide an inkjet recording material excellent in continuous paper feeding in an inkjet recording apparatus. As a result, in an inkjet recording material in which an ink receiving layer is provided on a support, the above problem was solved by containing a hydrazine derivative and a water-soluble polyvalent metal salt in the ink receiving layer.

The water-soluble polyvalent metal salt is preferably an organic acid metal salt, and the support is preferably acidic paper.

In a preferred mode, the pigment used in the ink receiving layer is made of amorphous silica.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The ink jet recording material of the present invention will be described in detail below.

The hydrazine derivative used in the present invention is
It is preferably represented by the following chemical formula 1.

[0017]

[Chemical 1]

In Chemical Formula 1, R _{1 to} R ₄ are independently a hydrogen atom, a substituted or unsubstituted aliphatic group, an aromatic group, a heterocyclic group, a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or iminomethylene. A group and the like are preferable. These may be linked to form a ring, or may be a polymer.

Examples of the above-mentioned substituent include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group,
Examples thereof include a hydrazino group, a carbonyl group and a carbamoyl group, and these substituents may further have another substituent.

A hydrazine derivative having a substituted or unsubstituted carbonyl group or sulfonyl group in at least one of R _{1 to} R ₄ is particularly preferable. Examples of the hydrazine derivative used in the present invention include the following compounds.

[0021]

[Chemical 2]

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

The content of the hydrazine derivative used in the present invention in the ink receiving layer is 0.1 to 50 mmol /
m ² is preferable, and more preferably 0.2 to 20 mmol / m ² . If it exceeds 50 mmol / m ² , the hue of the ink receiving layer changes or the hue balance of the image changes.

The water-soluble polyvalent metal compound used in the present invention is a water-soluble metal selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten and molybdenum. The salt may be a salt. Specifically, for example, calcium acetate, calcium chloride, calcium formate, calcium sulfate, sodium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, chloride Cupric, ammonium (II) chloride chloride dihydrate,
Copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium sulfate hexahydrate, amide nickel sulfate tetrahydrate, Aluminum sulfate, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfide, sulfuric acid Ferric, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zinc salicylate, zirconium acetate, zirconium chloride, zirconium chloride octahydrate, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate , Magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, Sodium enoic acid tungsten, 12 tungstophosphoric acid n-hydrate, dodecatungstosilicic acid 26-hydrate, molybdenum chloride, dodecamolybdophosphoric acid n-hydrate.

The water-soluble polyvalent metal salt used in the present invention is
Organic acid polyvalent metal salts are more preferred. Among the organic acid polyvalent metal salts, organic sulfonic acid metal salts, organic sulfuric acid ester metal salts are preferable, for example, benzene sulfonic acid metal salts, naphthalene sulfonic acid metal salts and the like are known, as the substituents to have these , Alkyl group, alkenyl group, hydroxyl group, mercapto group, nitro group, nitroso group,
Examples thereof include amino group, oxyamino group, hydrazino group, halogen group, aldehyde group, ketone group and carboxyl group. Further, it may have two or more different substituents. Of these, preferred are calcium toluene sulfonate, zinc toluene sulfonate, calcium phenol sulfonate, zinc phenol sulfonate, and zinc sulfosalicylate.

The water-soluble polyvalent metal salt used in the present invention means that it is dissolved in water at 20 ° C. in an amount of 1% by mass or more. The content of the water-soluble polyvalent metal salt used in the present invention in the ink receiving layer is preferably 0.1 to 50 mmol / m ^{2, and} more preferably 0.2 to 20 mmol / m ² . If it exceeds 50 mmol / m ² , the hue of the ink receiving layer changes or the hue balance of the image changes.

When both the hydrazine derivative used in the present invention and the water-soluble polyvalent metal salt are present in the ink receiving layer, the coating layer strength is increased. Although the reason is not clear, it is considered that there is an interaction between the hydrogen atom of the hydrazine derivative and the metal ion of the metal salt.

The support in the present invention is a paper containing pulp and filler as main components. As natural pulp,
Chemical pulp such as LBKP, NBKP, GP, PGW, R
Examples include mechanical pulp such as MP, TMC, CTMP, CMP and CGP, semi-chemical pulp, waste paper pulp such as DIP, and also non-wood pulp such as kenaf, bacus and cotton, and synthetic pulp. . These are 1
One kind or a mixture of two or more kinds can be used.

The support in the present invention is preferably acidic base paper containing natural pulp as a main component, or neutral base paper on a tab size press such as a sulfuric acid band solution, a sim sizer, an air knife coater, a blade coater, Pseudo-acidic base paper coated with a gate roll coater, bar coater, rod coater, roll coater, bill blade coater, short dwell blade coater, etc., among which acidic base paper is particularly preferable.

As a support for the ink jet recording material,
When so-called neutral paper containing natural pulp as the main component and mixed with heavy calcium carbonate or light calcium carbonate in the filler is used, the surface pH of the ink receiving layer shifts to the alkaline region with time. . This is because the filler is a solid alkali and affects the pH of the entire inkjet recording material including the ink receiving layer. The ink receiving layer is preferably acidic, that is, has a pH of 3 to 6.5. If the surface pH exceeds 6.5, the image storability is deteriorated. When an acidic base paper is used as the support in the present invention,
Not only is the coating strength high and continuous feeding is excellent,
An ink jet recording material having good image storability can be obtained.

In the present invention, the surface pH of the ink receiving layer
J. TAPPI paper pulp test method No. According to the method described in 6, a drop of a pH indicator is dropped on the surface of the test piece, and the color of the extract is measured by a standard color change table or a single drop extraction method in which the pH is determined by comparing with the pH standard color change solution.

The support used in the present invention includes, in addition to conventionally known fillers generally used in papermaking, a binder (water-soluble polymer), an internally added sizing agent, a paper-strengthening agent, a fluorescent agent, if necessary. One or more kinds of various additives such as a whitening agent, a yield improving agent and a coloring agent such as a dye or a pigment may be mixed.

When an internally added colorant is used in the support of the present invention, a direct dye, a basic dye, a reactive dye, a water-soluble dye typified by an edible pigment, a colored inorganic pigment such as a yellow red orange color, Pigments such as colored organic pigments and azo organic pigments are used, and yellow dyes and pigments are particularly preferable.

The ink-receiving layer according to the present invention is absorptive, image reproducible and colored for inks containing dyes and pigments used in commercially available ink jet recording devices (ink jet printers, ink jet plotters, ink jet proofers, etc.). And a binder (water-soluble polymer) as main components. Further, in the case of being applied to an ink jet recording system in which dye ink is also used, it is preferable to contain a cationic compound in addition to the above. Further, as other additives, pigment dispersants, thickeners, leveling agents, coloring dyes, coloring pigments, fluorescent whitening agents, ultraviolet absorbers, antioxidants, surfactants, defoaming agents, defoaming agents, Even if various additives such as a foaming agent, a penetrating agent, a release agent, an antiseptic agent, an antifungal agent, a waterproofing agent, a wet paper strength enhancer, a dry paper strength enhancer and a pH adjusting agent are added in an appropriate combination. good.

Examples of pigments used in the ink receiving layer of the present invention include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc carbonate, chisan white, silicic acid. Aluminum, diatomaceous earth, calcium silicate,
White inorganic pigments such as magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrohalosite, magnesium carbonate, magnesium hydroxide, styrene plastic pigment, acrylic One or more types of white pigments such as organic plastic pigments, polystyrene, microcapsules, urea resins, and organic pigments of melamine resins can be used. Among them, porous inorganic pigments are preferable, and porous synthetic amorphous silica, porous magnesium carbonate, porous alumina and the like can be mentioned, and porous synthetic amorphous silica having a large pore volume is particularly preferable.
Usually, the average particle size of these pigments is preferably in the range of 0.1 to 20 μm. When amorphous silica is used in the present invention,
The coating layer has high strength, excellent continuous feeding property, good image storability, and high ink absorbency.

Examples of the binder (water-soluble polymer) used in the ink-receiving layer of the present invention include natural polymer substances such as potato starch, sweet potato starch, wheat starch, tapioca starch, and starch such as corn starch, and laminaran. , Seaweed mannan, fungus, Irish moss, agar, and those obtained from algae such as alginate, grated yam, yam, mannan, quince seed, pectin, tragacanth gum, karaya gum, xanthine gum, guar gum,
Locust bean gum, tamarind seed gum, gum arabic, carob gum, benzoin gum and other plant mucilages, dextran, glucan, xanthan gum, homopolysaccharides such as levan, and succinoglucan, pullulan, curdlan, xanthan gum, etc. Examples thereof include microbial mucilages such as heterosaccharides, glue, gelatin, casein, and proteins such as collagen.

As the semi-natural product (semi-synthetic product), propylene glycol alginate, viscose,
Fiber cellulose derivatives such as methyl cellulose, ethyl cellulose, methyl ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl ethyl cellulose, carboxymethyl hydroxyethyl cellulose, and hydroxypropyl methyl cellulose phthalate, carboxymethyl guar gum, hydroxypropyl guar gum, and Examples thereof include modified gums such as hydroxyethyl guar gum, and processed or derivatives of the above natural polymer substances.

As the modified starch which is a semi-synthetic product, white dextrin, yellow dextrin, cultivated starch such as bridish gum, enzyme-modified dextrin such as enzyme dextrin and Schardinger dextrin, acid-decomposed starch such as solubilized starch, Oxidized starch such as dialdehyde starch, pregelatinized starch such as modified and non-modified pregelatinized starch,
Esterified starch such as starch phosphate, fatty acid starch, starch sulfate, nitrate nitrate, xanthate starch, and carbamic acid starch, hydroxyalkyl starch, carboxyalkyl starch, sulfoalkyl starch, cyanoethyl starch, allyl starch, benzyl starch, carbamyl Etherified starch such as ethyl starch and dialkylamino starch, methylol crosslinked starch, hydroxyalkyl crosslinked starch, phosphoric acid crosslinked starch, and crosslinked starch such as dicarboxylic acid crosslinked starch, starch polyacrylamide copolymer, starch polyacrylonitrile copolymer , Cationic starch polyacrylate copolymer,
Examples include cationic starch vinyl polymer copolymers, starch styrene maleic acid copolymers, starch graft copolymers such as starch polyethylene oxide copolymers, and the like.

As the synthetic product, polyvinyl alcohol,
Silyl-modified polyvinyl alcohol, partially acetalized polyvinyl alcohol, allyl-modified polyvinyl alcohol, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl isobutyl ether and other modified polyvinyl alcohol, polyacrylic acid salts, polyacrylic acid ester partially saponified products, polymethacrylic acid Salts, polyacrylic acid derivatives and polymethacrylic acid derivatives such as polyacrylic amide, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, vinylpyrrolidone vinyl acetate copolymer, styrene butadiene copolymer (SBR), nitrile butadiene copolymer ( NBR),
Examples thereof include a styrene acrylic acid ester copolymer, a styrene maleic acid copolymer, a styrene crotonic acid copolymer, and a vinyl chloride-containing copolymer. The above binders (water-soluble polymers) may be used alone or in combination of two or more.

The cationic compound used in the ink receiving layer of the present invention is a salt insoluble in the sulfonic acid group, carboxyl group, amine group and the like in the water-soluble direct dye or water-soluble acidic dye which is a water-soluble ink dye component. Secondary amine, which forms
Examples thereof include compounds containing a primary amino or quaternary ammonium salt. The cationic compounds may be used alone or in combination of two or more.

The layer structure of the ink receiving layer of the present invention may be a single layer or a laminated layer on the support. In the case of a laminated structure, all layers may be layers having the same composition, or may be a laminated structure with layers composed of other components. In the case of lamination, the hydrazine derivative and the water-soluble polyvalent metal salt may be present in either layer or may be contained in two or more layers.
It is preferably the outermost layer from the viewpoint of continuous sheet feeding of the inkjet recording apparatus.

The coating amount of the ink receiving layer of the present invention is as follows.
It is preferably in the range of 1 to 40 g / m ² . If the coating amount is less than 1 g / m ² , the ink absorbability by the ink receiving layer is not sufficient, so uneven absorption occurs and the ink jet performance is adversely affected. When it exceeds 40 g / m ² , the adhesive strength between the ink receiving layer and the support is lowered.

As the method for coating and impregnating the ink receiving layer on the support according to the present invention, slide popper coating method, curtain coating method, extrusion coating method, air knife coating method, blade coating method, roll coating method, A rod bar coating method, a gravure coating method, a size press coating method, a spray coating method and the like can be mentioned. These coating methods can be performed on-machine or off-machine. Moreover, you may finish using a calendar after coating or impregnation. Examples of the calendar method include a machine calendar method, a TG calendar method, a super calendar method, a soft calendar method, an embossing calendar method and the like.

The thickness of the ink jet recording material of the present invention is preferably about 50 to 300 μm. If it exceeds 300 μm, the rigidity becomes high and the flexibility of the recording material is lacking, so that the transportability in the ink jet recording apparatus is deteriorated. Further, if it is less than 50 μm, the printing characteristics (cockling, ink absorption, etc.) are adversely affected, and
Since the rigidity of the inkjet recording material decreases, the transportability in the inkjet recording apparatus decreases.

The ink referred to in the present invention means the following colorants,
It is a recording liquid consisting of a solvent and other additives.

Examples of the colorant for the ink include direct dyes, basic dyes, reactive dyes, dyes such as water-soluble dyes represented by food dyes, colored inorganic pigments such as carbon black, phthalocyanine organic pigments, and azo. Examples include pigments such as organic pigments.

The solvent of the ink is water and various water-soluble organic solvents. For example, alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, dimethylformamide, dimethylacetamide. Amides such as acetone, ketones or ketone alcohols such as acetone and diacetone alcohol, ethers such as tetrahydrofuran and dioxane, polyalkylene glycols such as polyethylene glycol and polyouropylene glycol, ethylene glycol, propylene glycol, butylene glycol and tri Alkyle such as ethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol 2-6 alkylene glycol such groups, glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether, and the like. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether are preferable. Other additives include, for example, a pH adjusting agent, a sequestering agent, an antifungal agent, a viscosity adjusting agent, a surface tension adjusting agent, a wetting agent, a surfactant, and a rust preventive agent.

[0050]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Also,
Parts and% shown in the examples are parts by mass and% by mass, unless otherwise specified.

<Preparation of Support A> 80 parts of broadleaf bleached kraft pulp (LBKP, freeness 370 mlcsf) and softwood bleached kraft pulp (NBKP, freeness 400 mlcs)
f) A raw paper having a basis weight of 100 g / m ² is made from a slurry composed of 20 parts, 13 parts of talc, 3 parts of a sulfuric acid band, 0.2 part of a commercial rosin sizing agent and 0.3 part of cationic starch with a Fourdrinier paper machine. Then, at the time of papermaking, oxidized starch was attached at a solid content of 2 g / m ² using a size press machine to produce a support A of acidic base paper. The pH of the surface of this base paper was 4.6.

<Preparation of Support B> 80 parts of broad-leaved tree bleached kraft pulp (LBKP, freeness 370 mlcsf) and softwood bleached kraft pulp (NBKP, freeness 400 mlcs)
f) 20 parts, 13 parts ground calcium carbonate, 1 part cationic starch, 0.08 part alkyl ketene dimer sizing agent and polyalkylene polyamine epichlorohydrin resin 0.
Basis weight of 100 with a Fourdrinier paper machine from 4 parts slurry
and papermaking base paper of g / m ^2, to produce a support B neutral base paper 2 g / m ² deposited was in a solid content of oxidized starch by a size press apparatus during papermaking. The pH of the surface of this base paper was 7.8.

<Ink Receiving Layer Coating Liquid A> Amorphous silica fine particles (Mizukasil P78A:
Secondary particle diameter 3.3μ: 100 parts of Mizusawa Chemical Co., Ltd., 20 parts of polyvinyl alcohol (R1130: Kuraray Co., Ltd.), 20 parts of cationic dye fixing agent (SUMIREZ Resin 1001: Sumitomo Chemical Co., Ltd.) were mixed, Ink-receiving layer coating liquid A was used.

<Ink Receiving Layer Coating Liquid B> Primary Particle Diameter 10
-20 nm colloidal silica (Snowtex O, Nissan Chemical Co., Ltd.) 20 parts, amorphous silica fine particles (Mizukasil P78A: secondary particle diameter 3.3μ: Mizusawa Chemical Co., Ltd.) 100
20 parts of polyvinyl alcohol (PVA117: manufactured by Kuraray Co., Ltd.) and 20 parts of a cationic dye fixing agent (SUMIREZ RESIN 1001: manufactured by Sumitomo Chemical Co., Ltd.) to prepare an ink receiving layer coating liquid B.

<Ink receiving layer coating liquid C> 0.5 mmol / m of the hydrazine derivative (3) is added to the ink receiving layer coating liquid A.
^A proper amount of ² was mixed to obtain an ink receiving layer coating liquid C.

<Ink Receiving Layer Coating Liquid D> The ink receiving layer coating liquid A contains basic polyaluminum hydroxide (Purachem W).
T: manufactured by Riken Green Co., Ltd.) was mixed in an appropriate amount so as to be 0.5 mmol / m ² to obtain an ink receiving layer coating liquid D.

<Ink Receiving Layer Coating Liquid E> 0.5 mmol / m of the hydrazine derivative (3) was added to the ink receiving layer coating liquid A.
² , base-based poly aluminum hydroxide (Purachem W
T: manufactured by Riken Green Co., Ltd.) was mixed in an appropriate amount so as to be 0.5 mmol / m ² to obtain an ink receiving layer coating liquid E.

<Ink receiving layer coating liquid F> 40 mmol / m ² of the hydrazine derivative (3) of the ink receiving layer coating liquid E
Ink receiving layer coating liquid F was used instead.

<Ink Receiving Layer Coating Liquid G> The ink receiving layer coating liquid E was replaced with the basic aluminum polyhydroxide (Purachem WT: manufactured by Riken Green Co., Ltd.) in place of 40 mmol / m ² to receive the ink. A layer coating liquid G was used.

<Ink Receiving Layer Coating Liquid H> 100 parts of amorphous silica fine particles (Mizukasil P50: secondary particle diameter 9.5 μ: manufactured by Mizusawa Chemical Co., Ltd.) as a pigment for the ink receiving layer, polyvinyl alcohol (R1130: Kuraray Co., Ltd.) 20 parts, cationic dye fixing agent (Sumireds resin 1001: manufactured by Sumitomo Chemical Co., Ltd.), hydrazine derivative (16) 0.5 mmol / m ² , zinc p-phenolsulfonate (manufactured by Kishida Chemical Co., Ltd.) Was mixed in an appropriate amount so as to be 0.5 mmol / m ² to obtain an ink receiving layer coating liquid H.

<Ink receiving layer coating liquid I> Amorphous silica fine particles (Finesil X60:
Secondary particle size 6.2μ: 100 parts by Tokuyama), polyvinyl alcohol (PVA117: by Kuraray) 25 parts,
20 parts of a cationic dye fixing agent (Sumired's resin 1001: manufactured by Sumitomo Chemical Co., Ltd.) and a hydrazine derivative (29) were added to 0.2 parts.
An appropriate amount of 5 mmol / m ² and zinc 5-sulfosalicylate (manufactured by Kanto Chemical Co., Inc.) was mixed at 0.5 mmol / m ² to prepare an ink receiving layer coating liquid I.

Examples 1 to 6 and Comparative Examples 1 to 4 The ink receiving layer shown in Table 1 was coated and dried on a support by a bar coater so that the dry coating amount was 15 g / m ² . 6 and Comparative Examples 1 to 4 were obtained.

The ink jet recording materials prepared in the above Examples and Comparative Examples were evaluated by the following evaluation methods, and the results are shown in Table 1.

(1) Coating Layer Strength (1-1) Measurement of Coefficient of Static Friction of 100th Sheet between Ink-Receiving Layer Side Surface of Inkjet Recording Material and Paper Feed Roller Friction Coefficient Measuring Device According to ASTM D-1894-63 (AB-401, manufactured by Tester Sangyo), 23 ° C
Under a 50% RH environment, the coefficient of static friction between the surface of the inkjet recording material on the ink receiving layer side and the paper feed roller was determined according to JIS P8147. An A4 size seed is used as the inkjet recording material, and an Epson inkjet printer (PM is used as the elastic sheet.
750C) paper feed roller processed into a sheet shape, and the inkjet recording material side is 1000 mm /
The static friction force (mN) of the 100th sheet after moving at the speed of minute
Was measured. The static friction coefficient was calculated by the following formula. Static friction coefficient = static friction force (mN) ÷ weight vertical load (g)
× 9.8 It was judged that continuous feedability was obtained when the static friction coefficient value exceeded 2.

(1-2) Falling of powder After performing the measurement of (1-1), the powder of the ink receiving layer attached to the paper feed roller was visually judged. ○: Almost no powder is observed. Δ: Some powder is observed. X: Adhesion of powder is clearly recognized. The powder drop that does not affect the continuous feeding property is evaluated as ◯ and Δ.

(2) Image hue Epson inkjet printer (PM750
Solid printing of BK, Y, M, and C was performed according to C), and the difference in color was visually determined using Comparative Example 1 as a reference (◯). ◯: Almost no difference in color is recognized. Δ: A slight difference in color is recognized. X: Clearly a difference in color is recognized. The difference in color has no problem in practical use in the evaluations of ◯ and Δ.

(3) Evaluation of image storability As an evaluation of image storability, light resistance was evaluated. Solid printing was performed in the same manner as in (2) above, and after irradiation with a Suntest CPS photobleaching tester manufactured by Atlas at 600 W / m ² for 30 hours, the density of the printed portion was measured, and the image residual ratio (density after irradiation / density after irradiation / The concentration before irradiation) was determined and the one with the lowest residual rate was shown. 80% or more is a level at which there is no practical problem.

[0068]

[Table 1]

As is apparent from Table 1 above, in Examples 1 to 6 containing the hydrazine derivative and the water-soluble polyvalent metal salt, the coating layer strength was high and the static friction coefficient of the 100th sheet was high.
Further, it is excellent in image hue and image storability. On the other hand, in Comparative Examples 1 to 4 containing no hydrazine derivative and / or water-soluble polyvalent metal salt, the coating layer strength was not sufficient, and the static friction coefficient of the 100th sheet was low.

[0070]

By using the ink jet recording material of the present invention, it is possible to provide an ink jet recording material having a high coating strength of the ink receiving layer and excellent continuous feeding property in an ink jet recording apparatus. It was

Claims (4)

[Claims] 1. An ink jet recording material comprising an ink receiving layer provided on a support, wherein the ink receiving layer contains a hydrazine derivative and a water-soluble polyvalent metal salt. 2. The ink jet recording material according to claim 1, wherein the water-soluble polyvalent metal salt is an organic acid metal salt. 3. The ink jet recording material according to claim 1, wherein the support is acid paper. 4. The ink jet recording material according to claim 1, wherein the pigment used in the ink receiving layer is made of amorphous silica.