JP2003011489A - Ink jet recording material and ink for ink jet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording material, improved in high luster like a photograph, high ink absorbing property and storage stability, and ink for ink jet recording, which is improved in the storage stability. SOLUTION: The ink jet recording material contains at least one kind of hydrazine compound replaced by an oxaryl group, a thiocarbonyl group, a sulfinyl group, a phosphoryl group or a group shown by -C(=NR0 ) in the ink receptive layer of the same. In this case, R0 shows a hydrogen atom or a monovalent organic group.

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 an ink for ink jet recording, and more specifically, it has a photo-like high gloss, excellent ink absorbability, and improved storage stability after printing. The present invention relates to an inkjet recording material and an inkjet recording ink having improved storage stability after printing.

[0002]

2. Description of the Related Art As a recording material used in an ink jet recording system, a pigment such as amorphous silica or alumina and a water-soluble binder such as polyvinyl alcohol are provided on a support called ordinary paper or ink jet recording paper. A recording material having a porous ink absorbing layer is known.

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

Further, Japanese Patent Publication No. 3-56552 and Japanese Patent Laid-Open No. Hei 2
-188287, 10-81064, 10-1
19423, 10-175365, 10-19.
No. 3776, No. 10-203006, No. 10-217.
No. 601, No. 11-20300, No. 11-20306
JP-A-11-34481 and the like disclose the use of synthetic silica fine particles by a vapor phase method (hereinafter referred to as vapor phase silica). The vapor-phase method silica is an ultrafine particle having an average primary particle diameter of several nm to several tens of nm, and is characterized by high gloss. Further, Japanese Patent Laid-Open No. 2-2
766771, 3-251488, 5-16517 and the like disclose recording materials using alumina hydrate.

In recent years, with the demand for photo-like recording sheets, the glossiness has become more and more important, and polyolefin resin-coated paper (paper whose both surfaces are laminated with a polyolefin resin such as polyethylene) or polyester film, etc. A recording material in which an ink receiving layer mainly composed of vapor phase silica, alumina or the like is coated on the water resistant support is used advantageously.

However, since the porous recording material using inorganic fine particles such as vapor-phase method silica is porous,
There is a problem that the printed image is easily discolored during storage after printing. That is, there is a big problem that discoloration or fading easily occurs due to light or a trace gas in the atmosphere.
In addition, in the water-resistant support, unlike the conventionally used paper support, since the support itself has no ink absorbing ability, the porosity of the porous recording layer is increased and the coating amount is increased. Therefore, it is necessary to secure the ink absorption capacity. As a result of such a design, the above-described image discoloration problem has become particularly serious.

Many proposals have been made in the past for the purpose of suppressing such discoloration and fading and improving the storability of printed images. For example, JP-A-57-74193
No. 57-87988 and No. 62-261478, a method using an ultraviolet absorber is also disclosed in JP-A-57-
74192, 57-87989, 60-727.
No. 85, No. 61-146591, No. 62-17038.
No. 1, 62-61477, JP-A-3-13376.
No. 7-314881, No. 7-314882, No. 8-25796, No. 9-267544 and the like describe methods using an antioxidant or an anti-fading agent.
However, all of these methods have an adverse effect such that the discoloration / fading prevention effect is insufficient, or even if the discoloration prevention effect is obtained, the coloring itself or the recording dye is discolored immediately after printing. There are many things that come out, and the current situation is that they have not reached the level of practical application. As described above, in the ink jet recording material having the porous ink receiving layer, the storability of the printed image is a particularly important issue, and an urgent countermeasure has been desired.

[0008]

Therefore, an object of the present invention is to provide an inkjet recording material and an inkjet recording ink having improved photo-like high gloss, high ink absorption, high water resistance and storage stability. Especially.

[0009]

The above object of the present invention is to provide an ink receiving layer, particularly a porous ink receiving layer containing inorganic fine particles, with an oxalyl group, a thiocarbonyl group, a sulfinyl group, a sulfonyl group, a phosphoryl group, Or -C (=
An inkjet recording material comprising at least one hydrazine compound substituted with a group represented by NR ₀ )-, particularly preferably the above general formula [I],
It was achieved by an inkjet recording material characterized by containing at least one compound represented by [II] and [III]. Further, the same effect can be obtained by including these compounds in the ink.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The inkjet recording material of the present invention has at least one ink receiving layer, and the ink receiving layer mainly contains inorganic fine particles, even if it is a so-called void type,
A swelling type which mainly contains a water-soluble polymer may be used. In the present invention, the former type is preferable.
The above-mentioned void type allows ink to be absorbed into the voids formed in the film, and it is necessary to increase the void volume in order to exhibit high ink absorbency. Therefore, it is necessary to coat a relatively large amount of inorganic fine particles on the support, and the amount of the hydrophilic binder is preferably reduced in order to increase the porosity.

The inorganic fine particles used in the present invention include:
Light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate,
Satin white, aluminum silicate, diatomaceous earth, calcium silicate, synthetic silica, alumina, alumina hydrate,
Examples thereof include magnesium silicate, lithopone, zeolite and magnesium hydroxide. Among these, synthetic silica and alumina fine particles (alumina, alumina hydrate) are preferable, and vapor phase silica and alumina fine particles are particularly preferable. These may be used alone or in combination. In combination, they may be mixed in the same layer or may be formed in separate layers and used in a laminated form.

The vapor-phase process silica preferably used in the present invention is also called dry process silica and is generally produced by a flame hydrolysis method. Specifically, a method in which silicon tetrachloride is burnt together with hydrogen and oxygen is generally known. Vapor phase silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Corp., and can be obtained. In general, vapor-phase method silica is aggregated into secondary particles having appropriate voids.
It is preferable that the particles are pulverized and dispersed by an ultrasonic wave, a high-pressure homogenizer, an opposed collision type jet pulverizer or the like until the secondary particles of about 0 to 300 nm are obtained, because the ink absorbability and glossiness are good.

Alumina fine particles (alumina and alumina hydrate) preferably used in the present invention are aluminum oxide and hydrates thereof and may be crystalline or amorphous.
Those having an irregular shape, a spherical shape, a plate shape, or the like are used. As the alumina, γ-alumina which is a γ-type crystal of aluminum oxide is preferable. γ-alumina can reduce the primary particles to about 10 nm,
Usually, a secondary particle crystal of several thousands to tens of thousands nm is subjected to ultrasonic waves, a high pressure homogenizer, a counter collision type jet crusher, etc.
Those pulverized to about 300 nm can be preferably used. Alumina hydrate is Al ₂ O ₃ · nH ₂ O (n = 1 to 1
It is represented by the constitutive equation of 3). When n is 1, it represents an alumina hydrate having a boehmite structure, and when n is more than 1 and less than 3, it is an alumina hydrate having a pseudo-boehmite structure. Hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali,
It can be obtained by a known production method such as hydrolysis of an aluminate.

The average particle size of the primary particles of the fumed silica, alumina, and alumina hydrate of the present invention means that the dispersed particles exist within a certain area by observing the dispersed particles with an electron microscope.
The diameter of a circle equal to the projected area of each individual particle was determined as the particle size of the particle. The average particle size of the primary particles of the vapor-phase method silica used in the present invention is 5 to 50 nm, preferably 5 to 50 nm.
It is 30 nm. The average particle diameter of the primary particles of the alumina and alumina hydrate of the present invention is 10 to 50 nm, preferably 10 to 30 nm.

In the present invention, the amount of the inorganic fine particles used in the recording layer is preferably 8 g / m ² or more, and 10 to 30 g / m ^2.
The range of m ² is more preferable. If it is less than this range, the ink absorbency is inferior, and if it is more than this range, the strength of the ink receiving layer is lowered, which tends to cause a problem during production or use.

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

In the present invention, as the hydrophilic binder used together with the inorganic fine particles, various known binders can be used, but a hydrophilic binder which has high transparency and can achieve higher ink permeability is preferably used. In using the hydrophilic binder, it is important that the hydrophilic binder does not swell and block the voids at the initial penetration of the ink. From this viewpoint, a hydrophilic binder having a low swelling property at around room temperature is preferable. Used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol.

Among the polyvinyl alcohols, those partially or completely saponified with a saponification degree of 80% or more are particularly preferable. Those having an average degree of polymerization of 200 to 5000 are preferable.

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

In the present invention, it is preferable to use a crosslinking agent (hardening agent) together with the above hydrophilic binder. Specific examples of the crosslinking agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,
3,5-triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, US Patent No. 2,73
N-methylol compounds as described in US Pat. No. 2,316, isocyanates as described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280 and 2,983.
No. 611, aziridine compounds, US Pat. No. 3,100,704, carbodiimide compounds, US Pat. No. 3,091,537, epoxy compounds, mucochloric acid, halogen carboxaldehydes, There are dioxane derivatives such as dihydroxy dioxane, chromium alum, zirconium sulfate, inorganic cross-linking agents such as boric acid and borate, and these may be used alone or in combination of two or more. Among these, boric acid or borate is particularly preferable.

According to a preferred embodiment of the present invention, the surface pH of the membrane is 3 to 3 in combination with the inorganic fine particles on the water resistant support.
6, the pH of the ink-receptive layer having a pH of 3 to 5.5, by containing the compound of the present invention represented by the general formula [I], [II], or [III], glossiness, ink absorption, and The storability after printing can be significantly improved.

According to another preferred embodiment of the present invention, the film surface p is combined with the fumed silica or alumina fine particles.
By containing the cationic compound and the compound of the present invention represented by the general formula [I], [II], or [III] in the ink receiving layer having H3 to 6 and preferably pH 3 to 5.5, glossiness can be improved. The ink absorbency, and the storage stability after printing can be significantly improved.

In the general formulas [I] to [III], A represents an oxalyl group, a thiocarbonyl group, a sulfinyl group, a sulfonyl group, or a group represented by -C (= NR ₀ )-. R _{1 to} R ₃ each independently represent a hydrogen atom, an optionally substituted aliphatic group, an aromatic group, a heterocyclic group, an ester group, or an acyl group, and R ₁ and R ₂ or R ₁ and R ₃ May combine with each other to form a heterocycle. R ₄ and R ₀ represent a hydrogen atom or a monovalent organic group.

Specific examples of R _{1 to} R ₃ are each independently a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, a chloroethyl group, a hydroxyethyl group and a benzyl group. , Allyl group,
Alkenyl group such as 3-butenyl group, phenyl group, naphthyl group, 4-methylphenyl group, 3-aminophenyl group, 2-bromophenyl group, 3-chlorophenyl group, 4
An aryl group such as a fluorophenyl group and a 4-hydroxyphenyl group, a 2-pyridyl group, a 4-piperidinyl group,
Heterocyclic group such as 2-benzothiazolyl group, ester group such as alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, 3-chlorophenoxycarbonyl group, etc.), acetyl group And acyl groups such as a propionyl group, a hexanoyl group, and a benzoyl group. Examples of the heterocycle formed by R ₁ and R ₂ or R ₁ and R ₃ bonded to each other include a pyrrolidine ring, a piperidine ring, a pyrazine ring and a morpholine ring.

Specific examples of R ₄ and R ₀ include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a cyclohexyl group, a chloroethyl group, a hydroxyethyl group and a benzyl group, an alkenyl such as an allyl group and a 3-butenyl group. Group, phenyl group, naphthyl group, 4-methylphenyl group, 3-aminophenyl group, 2-bromophenyl group, 3-chlorophenyl group, 4-fluorophenyl group, aryl group such as 4-hydroxyphenyl group, 2-pyridyl group Group, 4-piperidinyl group, heterocyclic group such as 2-benzothiazolyl group,
Alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and 4-chlorophenoxy group,
Examples thereof include amino groups such as methylamino group and dimethylamino group.

Among the above, A is preferably an oxalyl group, and those in which R ₁ and R ₂ are simultaneously an alkyl group and those in which R ₁ and R ₂ are bonded to form a ring are preferred. preferable.

Specific examples of the compounds of the general formulas [I] to [III] used in the recording material of the present invention include those shown below, but the present invention is not limited thereto. Not something.

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

General formulas [I] to [II] used in the present invention
The content of the compound of [I] in the ink receiving layer is 0.
1 to 50 mmol / m ² is preferable, and 0.2 to 20 mmol / m ² is more preferable.

Examples of the cationic compound used in the present invention include cationic polymers and water-soluble metal compounds. As the cationic polymer, polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, 5
9-33176, 59-33177, 59-1
No. 55088, No. 60-11389, No. 60-499.
No. 90, No. 60-83882, No. 60-109894
No. 62-198493, No. 63-49478,
63-115780, 63-280681, JP-A-1-40371, 6-234268, 7-.
Polymers having a primary to tertiary amino group and a quaternary ammonium group described in JP-A-125411 and JP-A-10-193776 are preferably used. The molecular weight of these cationic polymers is preferably 5,000 or more, more preferably about 5,000 to 100,000.

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

Examples of the water-soluble metal compound used in the present invention include water-soluble polyvalent metal salts. Examples thereof include water-soluble salts of metals selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten and molybdenum. Specifically, for example, calcium acetate, calcium chloride, calcium formate, calcium sulfate, barium acetate, barium sulfate, barium phosphate, manganese chloride, manganese acetate, manganese formate dihydrate, manganese ammonium sulfate hexahydrate, chloride chloride. Dicopper, ammonium chloride copper (II) dihydrate, copper sulfate, cobalt chloride,
Cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium ammonium hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum sulfite, Aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate,
Ferrous bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, zinc bromide, zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zirconium acetate, zirconium chloride, chloride Zirconium oxide octahydrate, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, sodium citrate tungsten, 12 tungstophosphate n Hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate and the like can be mentioned.

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

The basic polyaluminum hydroxide compound
Means that the main component is represented by the following formula, for example, [Al₆(O
H)₁₅]³⁺, [Al₈(OH)₂₀]⁴⁺, [Al₁₃(O
H)₃₄] ⁵⁺, [Al_{twenty one}(OH)₆₀]³⁺Bases such as,
Water-soluble, stable and containing polynuclear polycondensation ions
Of polyaluminum hydroxide.

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

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

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

In the present invention, the content of the water-soluble metal compound in the ink receiving layer is 0.
It is preferably 1 to 10% by weight, more preferably 1 to 5% by weight.

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

In the present invention, the film surface pH of the ink receiving layer
J. Surface pH measured after 30 seconds with distilled water according to the method described in TAPPI Paper Pulp Test Method N0.49.

The pH of the ink receiving layer is preferably adjusted at the stage of the coating liquid, but since the pH of the coating liquid and the film surface pH in the coated and dried state do not necessarily match, the coating liquid and the film surface pH It is necessary to previously obtain the relationship between and by an experiment or the like in order to obtain a predetermined film surface pH. The pH of the ink receiving layer coating liquid is determined by appropriately combining acid or alkali. As the acid, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and organic acids such as acetic acid, citric acid and succinic acid are used, and as the alkali, sodium hydroxide, aqueous ammonia, potassium carbonate, trisodium phosphate. Alternatively, as the weak alkali, an alkali metal salt of a weak acid such as sodium acetate is used.

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

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

In the present invention, the ink receiving layer further comprises
Various known additives such as coloring dyes, coloring pigments, fixing agents for ink dyes, ultraviolet absorbers, antioxidants, pigment dispersants, defoamers, leveling agents, preservatives, optical brighteners, viscosity stabilizers, etc. Can also be added.

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

The base paper constituting the resin-coated paper preferably used in the present invention is not particularly limited, and commonly used paper can be used, but more preferably, it is smooth as used for a photographic support. Raw base paper is preferred. As the pulp constituting the raw paper, one kind or a mixture of two or more kinds of natural pulp, recycled pulp, synthetic pulp and the like is used. This base paper has a sizing agent, a paper strengthening agent, a filler, an antistatic agent, an optical brightening agent, which is generally used in papermaking,
Additives such as dyes are blended.

Further, a surface sizing agent, a surface paper strength agent, a fluorescent whitening agent, an antistatic agent, a dye, an anchoring agent or the like may be applied on the surface.

There is no particular limitation on the thickness of the base paper, but it is preferable that the paper has good surface smoothness such as compression by applying pressure with a calendar or the like during or after paper making, and the basis weight is 30. ˜250 g / m ² is preferred.

As the resin for the resin-coated paper, a polyolefin resin or a resin curable with an electron beam can be used.
The polyolefin resin is a homopolymer of olefins such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or a copolymer of two or more olefins such as ethylene-propylene copolymer and a mixture thereof. Various densities and melt viscosity indexes (melt indexes) can be used alone or in combination.

In the resin of the resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid 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, Phthalocyanine Blue, Cobalt Violet, Fast Violet, Manganese Purple It is preferable to add various additives such as magenta pigments and dyes, fluorescent whitening agents, and ultraviolet absorbers in an appropriate combination.

The resin-coated paper, which is a support preferably used in the present invention, is a polyolefin resin, which is produced by a so-called extrusion coating method in which a resin melted by heating is cast on a running base paper, and both sides of the resin are coated with the resin. Is covered by. 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 the resin is irradiated with an electron beam to cure and coat the resin. Further, it is preferable to perform activation treatment such as corona discharge treatment or flame treatment on the base paper before coating the base paper with the resin. The surface (surface) of the support to which the ink receiving layer is applied has a glossy surface, a matte surface or the like depending on the application, and the glossy surface is particularly predominantly used. It is not necessary to coat the back surface with a resin, but it is preferable to coat the resin from the viewpoint of preventing curling. 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, if necessary. The thickness of the resin coating layer is not particularly limited, but it is generally coated on the surface or both front and back sides with a thickness of 5 to 50 μm.

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

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

In the present invention, the ink jet recording material may be provided with an ink absorbing layer, an ink fixing layer, an intermediate layer, a protective layer and the like in addition to the layer containing at least one inorganic fine particle. For example, a water-soluble polymer layer may be applied as a lower layer, and a swelling layer or a porous layer may be applied as an upper layer. In particular, by providing a porous upper layer of alumina hydrate with a coating amount smaller than that of the vapor-phase-process silica of the lower layer, it is possible to obtain an ink jet recording material having high printing density and excellent storage stability.

When the compounds of the general formulas [I] to [III] of the present invention are contained in the ink for ink jet recording, the preservability after printing can be greatly improved. The content is 0.05 to 15 in the ink composition.
About 10% by weight is preferable, and about 0.1 to 10% by weight is more preferable. The coloring material used in the ink may be either a dye or a pigment, but it is particularly effective in the case of a dye.

As the dye, various dyes such as direct dyes, acid dyes, food dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, and reactive disperse dyes can be used.

For example, examples of dyes include C.I. I. Direct Black -4, -9, -11, -17, -19,-
22, -32, -80, -151, -154, -16
8, -171, -194 and -195, C.I. I. Direct Blue-1, -2, -6, -8, -22, -34,
-70, -71, -76, -78, -86, -142,
-199, -200, -201, -202, -203,
-207, -218, -236 and -287, C.I. I.
Direct Red-1, -2, -4, -8, -9, -1
1, -13, -15, -20, -28, -31, -3
3, -37, -39, -51, -59, -62, -6
3, -73, -75, -80, -81, -83, -8
7, -90, -94, -95, -99, -101, -1
10, -189 and -227, C.I. I. Direct Yellow-1, -2, -4, -8, -11, -12, -2
6, -27, -28, -33, -34, -41, -4
4, -48, -86, -87, -88, -135, -1
42 and -144, C.I. I. Food Black-1 and-
2, C.I. I. Acid Black-1, -2, -7, -1
6, -24, -26, -28, -31, -48, -5
2, -63, -107, -112, -118, -11
9, -121, -172, -194 and -208, C.I.
I. Acid Blue-1, -7, -9, -15, -2
2, -23, -27, -29, -40, -43, -5
5, -62, -78, -80, -81, -90, -10
2, -104, -111, -185 and -254, C.I.
I. Acid Red-1, -4, -8, -13, -1
4, -15, -18, -21, -26, -35, -3
7, -52, -249 and -257, C.I. I. Acid Yellow-1, -3, -4, -7, -11, -12,-
13, -14, -19, -23, -25, -34, -3
8, -41, -42, -44, -53, -55, -6
1, -71, -76 and -79, Blodget cyan 1, Blodgett magenta 1, Blodgett magenta 1
T, Borjet Yellow 1G (above Zeneca
, AE-SF VP344, Duasyn Bri
lliant Red F3BSF VP180 (above Hoechst), Basacid Black X34
liquid, Basacid Black X38
liquid, Basacid Red495 liq
uid, Basacid Blue 752 liqu
id, Basacid Blue 624 liqui
d, Basacid Blue 765 liquid,
Basacid Yellow SE0840 liq
uid, Basacid Yellow SE0173
liquid, Basacid Yellow 09
9 liquid (above BASF), Special
Black SP liquid, Special
Black HF (above Bayer) etc. are mentioned.
These dyes may be used singly or in a mixture of two or more, and further, those which are toned in four custom colors such as cyan, magenta, yellow and black, as well as custom colors such as red, blue and green may be used.

It is also possible to use pigments such as carbon black, brilliant tokamin BS, lake carmine FB, brilliant fast scar red, diazo yellow, permanent red R, fast yellow 10G, phthalocyanine blue, blue lake, rhodamine. A rake or the like can be used.

The content of these coloring materials is in the range of 0.5 to 20% by weight, preferably 1 to 10 with respect to the total amount of ink.
% By weight.

As the water-soluble organic solvent used in the ink composition of the present invention, those which act as a moisturizer can be contained, and for example, ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, triethylene glycol, hexylene. Glycol, glycerin, 1,2,6-hexanetriol,
Polyhydric alcohols such as 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
Polyhydric alcohol derivatives such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether, basic solvents such as pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone and triethanolamine, alcohols such as ethanol, isopropyl alcohol, butyl alcohol and benzyl alcohol. And the like. These water-soluble organic solvents are preferably contained in the range of 1 to 40% by weight with respect to the total amount of ink.

The ink composition of the present invention may further contain the following organic solvent. That is, imidazole, methylimidazole, hydroxyimidazole,
Triazole, nicotinamide, dimethylaminopyridine, ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, lactamide, sulfolane, dimethylsulfoxide, 1,3-propanesartone, methyl carbamate, ethyl carbamate, 1 -Methylol-5,5-
Dimethylhydantoin, hydroxyethylpiperazine,
Piperazine, ethylene urea, propylene urea, ethylene carbonate, propylene carbonate, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, acetamide, formamide, dimethylformamide, N-methylformamide,
Dimethylacetamide and the like can be included.

In the ink composition of the present invention, a coloring material is dissolved,
In order to further stabilize the dispersed state, a surfactant, a dispersant, an inclusion compound or the like may be added. As the surfactant, any of nonionic, anionic, cationic and amphoteric surfactants may be used, but nonionic surfactants are particularly preferable. Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid. Examples thereof include esters and fatty acid alkylolamides. Examples of the anionic surfactant include alkylbenzene sulfonate, alkylnaphthalenesulfonate, formalin condensate of alkylnaphthalenesulfonate, higher fatty acid salt, higher fatty acid ester sulfate ester salt, higher fatty acid ester sulfonate, and higher alcohol. Examples thereof include sulfate ester salts of ethers, sulfonates, alkylcarboxylates of higher alkylsulfonamide, and sulfosuccinates. As the cationic surfactant, primary to tertiary amine salts, quaternary ammonium salts and the like can be used, and as the amphoteric surfactant, betaine,
Sulfobetaine, sulfate betaine and the like can be used.

In addition, water-soluble polymers containing acrylic acid / methacrylic acid / maleic acid or salts thereof as monomer components, polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, cellulose derivatives, cyclodextrins, macrocyclic amines. , Crown ethers, urea, acetamide and the like can be used. In addition, if necessary, a pH adjusting agent, an antifungal agent, a chelating agent, an antiseptic agent, a rust preventive agent, a viscosity adjusting agent, a conductive agent or the like may be added.

[0068]

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

Example 1 A 1: 1 mixture of bleached hardwood kraft pulp (LBKP) and bleached softwood pulp (NBSP) was beaten to 300 ml with Canadian standard freeness to prepare a pulp slurry. Alkyl ketene dimer as a sizing agent to 0.5% by weight of pulp,
1.0% by weight of polyacrylamide to the pulp, 2.0% by weight of cationized starch to the pulp, and 0.5% by weight of polyamide epichlorohydrin resin to the pulp as a strength agent, and diluted with water to 1%. It was made into a slurry. This slurry was made into paper by a Fourdrinier paper machine so as to have a basis weight of 170 g / m ² , dried and conditioned to obtain a base paper for polyolefin resin-coated paper. A polyethylene resin composition in which 10% by weight of anatase-type titanium was uniformly dispersed in 100% by weight of a low-density polyethylene resin having a density of 0.918 g / cm ³ was melted at 320 ° C. to 200 m / 35 μm in thickness
Extrusion coating was carried out so as to be, and extrusion coating was carried out using a cooling roller having a finely roughened surface. On the other side, a blended resin composition of 70 parts by weight of a high density polyethylene resin having a density of 0.962 g / cm ³ and 30 parts by weight of a low density polyethylene resin having a density of 0.918 was similarly melted at 320 ° C. Extrusion coating to 30 μm,
It was extrusion coated using a roughened cooling roll.

After the high-frequency corona discharge treatment was applied to the surface of the above polyolefin resin-coated paper, the undercoat layer was coated with gelatin.
A support was prepared by coating and drying so as to give 0 mg / m ² .

An aqueous solution containing vapor phase method silica and Charol DC902P was dispersed with a high pressure homogenizer, and polyvinyl alcohol or the like was added to prepare a coating solution for the ink receiving layer having the following composition. 18 minutes
An inkjet recording sheet was prepared by coating and drying so that the coating amount was g / m ² . Each recording sheet was adjusted so that the film surface pH of the ink receiving layer was 4.0.

<Recording Sheet 1> 100 parts of gas phase method silica (average primary particle size 7 nm, specific surface area by BET method 300 m ² / g) 100 parts Dimethyldiallylammonium chloride polycondensate 3 parts (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Product name Charol DC902P) Polyvinyl alcohol 25 parts (Product name: PVA235, manufactured by Kuraray Co., Ltd., saponification degree 88%, average degree of polymerization 3500) Boric acid 4 parts Basic polyaluminum hydroxide (Purachem WT manufactured by Riken Green Co., Ltd.) 2 parts Amphoteric surfactant 0.3 parts (Product name: SWAM AM-2150, made by Nippon Surfactant)

<Recording Sheet 2> 6 mmol / m ² of the compound (6) of the present invention was added to the ink receiving layer of the above-mentioned Recording Sheet 1.

<Recording Sheet 3> 3 mmol / m ² of the compound (15) of the present invention was added to the ink receiving layer of the above Recording Sheet 1.

<Recording Sheet 4> The compound (16) of the present invention was added to the ink receiving layer of the above-mentioned Recording Sheet 1 at 3 mmol / m ² .

<Recording sheet 5> The compound (21) of the present invention was added to the ink receiving layer of the above-mentioned recording sheet 1 in an amount of 3 mmol / m ² .

<Recording sheet 6> The compound (22) of the present invention was added to the ink receiving layer of the above-mentioned recording sheet 1 in an amount of 3 mmol / m ² .

<Recording sheet 7> The compound (25) of the present invention was added to the ink-receiving layer of the above recording sheet 1 in an amount of 3 mmol / m ² .

<Recording Sheet 8> 3 mmol / m ² of the compound (27) of the present invention was added to the ink receiving layer of the above-mentioned Recording Sheet 1.

<Recording Sheet 9> 2 mmol / m ² of the compound (29) of the present invention was added to the ink receiving layer of the above-mentioned Recording Sheet 1.

Each of the obtained ink jet recording sheets was evaluated for ink absorbency, water resistance, storage stability after printing (light resistance and gas resistance), and glossiness. The results are shown in Table 1.

<Ink absorbency> Using an ink jet printer (PM-800C manufactured by Seiko Epson Corporation),
C, M and Y were printed at 100% respectively, and immediately after printing, PPC paper was overlaid on the printing portion and lightly pressed, and the degree of ink transferred to the PPC paper was visually observed and evaluated according to the following criteria. . ◯: No transfer is performed. X: Transfer.

<Water resistance> A thin wire with a width of 100 μm is 100 μm
After printing at m intervals and left for 1 day, the plate was placed under the conditions of 35 ° C. and 90% relative humidity (RH) for 2 days, and then bleeding of fine lines was evaluated according to the following criteria. ◯: Almost no blurring, and the interval between fine lines is clear. Δ: There is bleeding, but the space between the thin lines is not completely crushed. X: Fine lines are blurred and there is no space between the fine lines.

<Light resistance> Using an inkjet printer (PM-800C manufactured by Seiko Epson Corporation), CYMK
After solid printing with each ink and irradiating at 600 W / m ² for 50 hours with a Suntest CPS photobleaching tester manufactured by Atlas, the density of the printed part was measured, and the image residual ratio (concentration after irradiation / before irradiation Of the CMYK images, and the one with the lowest residual rate was displayed.

<Gas resistance> After printing in the same manner as in the light resistance test, after exposure in air at room temperature for 4 months, the density of the printed portion was measured to determine the image residual ratio (density after exposure / density before exposure). ) Was obtained, and the CMYK image with the lowest residual rate was displayed.

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

[0087]

[Table 1] ──────────────────────────────────   Recording sheet Ink absorbency Water resistance Storage (%) Remarks                                 Light resistance Gas resistance ──────────────────────────────────     1 ○ ○ 62 60 Comparison     2 ○ ○ 77 78 The present invention     3 ○ ○ 84 87 The present invention     4 ○ ○ 82 84 The present invention     5 ○ ○ 81 81 The present invention     6 ○ ○ 82 85 The present invention     7 ○ ○ 79 81 The present invention     8 ○ ○ 79 80 The present invention     9 ○ ○ 80 81 The present invention ──────────────────────────────────

The glossiness of each recording sheet is 60 to 6
At 5%, it showed high gloss. As is clear from the above results, by using the compound having the structure of the general formulas [I] to [III] of the present invention, light resistance and gas resistance are improved while maintaining high ink absorption and high water resistance. To be done. That is, according to the present invention, ink absorbency, water resistance and storability are simultaneously improved, and a photo-like high gloss is obtained.

Example 2 The vapor-phase-method silica used in Example 1 had an average primary particle size of 15 n.
The same test was conducted except that the pseudo-boehmite in the form of a flat plate having m and an aspect ratio of 5 was replaced. As a result, almost the same results were obtained with respect to ink absorbency, storability and gloss.

Example 3 The same result as in Example 1 was obtained by the same test as in Example 1 except that a polyester film was used as the support in Example 1.

Example 4 The following inkjet recording ink was prepared. [Yellow ink-Y1]   Direct Yellow 86 2.0g   Diethylene glycol 22.2g   Glycerin 4.5g   Make up to 100 ml pure. [Magenta ink-M1]   Direct Red 227 1.8g   Glycerin 3.5g   Diethylene glycol monobutyl ether 21.5g   Make up to 100 ml pure. [Cyan ink-C1]   Direct Blue 199 2.4g   Ethylene glycol 16.1g   Glycerin 9.5g   Make up to 100 ml pure.

2.5 g of the compound (6) of the present invention was added to each of the inks Y1, M1 and C1 of the respective colors to prepare inks Y2 and M1.
2, C2 was obtained.

2.5 g of the compound (15) of the present invention was added to each of the inks Y1, M1 and C1 of the respective colors, and the ink Y3,
M3 and C3 were obtained.

2.5 g of the compound (16) of the present invention was added to each of the inks Y1, M1 and C1 of the respective colors, and the ink Y4,
M4 and C4 were obtained.

2.5 g of the compound (22) of the present invention was added to each of the inks Y1, M1 and C1 of the respective colors described above, and the ink Y5,
M5 and C5 were obtained.

Each of the obtained ink jet recording inks was evaluated for print density, ink absorbency, preservability after printing (light resistance and gas resistance), and glossiness. As the recording method, an inkjet printer (PM800C manufactured by Seiko Epson Corporation) was used, and the recording sheet 1 used in Example 1 was printed with C, M, and Y at 100%.

The same evaluation as in Example 1 was performed on the ink jet recording sheet prepared as described above.
The results are shown in Table 2.

[0098]

[Table 2] ───────────────────────────────────     Ink ink absorbency Water resistance Storage (%) Remarks                                   Light resistance Gas resistance ───────────────────────────────────     Y1 ○ ○ 75 86 Comparison     M1 ○ ○ 69 84 Comparison     C1 ○ ○ 87 68 Comparison     Y2 ○ ○ 82 87 The present invention     M2 ○○ 73 85 The present invention     C2 ○○ 90 78 The present invention     Y3 ○ ○ 88 90 The present invention     M3 ○○ 80 88 The present invention     C3 ○○ 92 82 The present invention     Y4 ○ ○ 87 89 The present invention     M4 ○ ○ 78 87 The present invention     C4 ○ ○ 90 82 The present invention     Y5 ○ ○ 83 88 The present invention     M5 ○○ 72 85 The present invention     C5 ○ ○ 89 81 The present invention ───────────────────────────────────

The glossiness is 60 to 6 for all recording sheets.
At 5%, it showed high gloss. From the above, it can be seen that the inclusion of the compound of the present invention in the ink improves the light fastness and gas fastness while maintaining high ink absorbency and high water resistance.

[0100]

INDUSTRIAL APPLICABILITY According to the present invention, a photo-like ink jet recording material and ink for ink jet recording having high ink absorbency, high water resistance, high gloss and improved storage stability can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 213/77 C07D 295/22 Z 295/22 C09D 11/00 C09D 11/00 B41J 3/04 101Y

Claims (9)

[Claims] 1. An ink receiving layer containing at least one hydrazine compound substituted with an oxalyl group, a thiocarbonyl group, a sulfinyl group, a sulfonyl group, a phosphoryl group, or a group represented by —C (═NR ₀ ) —. An ink jet recording material containing the same. Here, R ₀ represents a hydrogen atom or a monovalent organic group. 2. The inkjet recording material according to claim 1, wherein the hydrazine compound is a compound represented by the following general formula [I], [II], or [III]. [Chemical 1] [Chemical 2] [Chemical 3] (In the general formulas [I] to [III], A represents an oxalyl group, a thiocarbonyl group, a sulfinyl group, a sulfonyl group, or a group represented by -C (= NR ₀ )-. R ₁
To R ₃ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an ester group, or an acyl group, and R
₁ and R ₂ or R ₁ and R ₃ may combine with each other to form a heterocycle. R ₄ and R ₀ represent a hydrogen atom or a monovalent organic group. ) 3. The ink jet recording material according to claim 1, wherein the ink receiving layer contains inorganic fine particles. 4. The ink jet recording material according to claim 3, wherein the inorganic fine particles are fine particles of vapor grown silica or alumina having an average primary particle diameter of 30 nm or less. 5. The ink jet recording material according to claim 1, wherein the ink receiving layer is crosslinked with a crosslinking agent. 6. The ink jet recording material according to claim 1, which has a film surface pH of 3 to 6. 7. The inkjet recording material according to claim 1, further comprising a cationic compound. 8. The support according to claim 1, which is a water-resistant support.
7. The inkjet recording material according to any one of 7. 9. An inkjet recording ink containing at least one of the compounds represented by the general formulas [I], [II] and [III].