JP2008183824A - Ink jet recording medium, method for producing the same, and ink jet recording method - Google Patents

Abstract

An ink jet recording medium that has excellent surface shape, excellent ink absorbability, and suppresses the occurrence of bronzing even when an ink containing a highly associative dye is used, a method for producing the same, and ink jet recording Provide a method.
An ink receiving layer, or an ink receiving layer and a gloss developing layer are provided on a support, and the ink receiving layer, or the ink receiving layer and the gloss developing layer are collected, and the collected ink receiving layer, Alternatively, when the mixed sample of the ink receiving layer and the glossy expression layer is measured by solid ¹¹ B-NMR, A defined by the following formula (1) is 0.6 or less, and the ink receiving layer is: An ink jet recording medium, a method for producing the same, and an ink jet recording method, which are formed by applying a coating solution containing a boron compound and exhibiting reduced rate drying and then applying a basic solution.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm)
[Selection figure] None

Description

  The present invention relates to an ink jet recording medium, a method for producing the same, and an ink jet recording method using the ink jet recording medium.

In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the information systems have been developed and put into practical use.
Among the above recording methods, the inkjet recording method is capable of recording on various types of recording media, the hardware (device) is relatively inexpensive, compact, and excellent in quietness. Of course, it has been widely used in so-called home use.

In addition, with the recent increase in resolution of inkjet printers, it has become possible to obtain so-called photographic-like high-quality recorded matter. Furthermore, with the development of hardware (device), various recording sheets for ink jet recording have been developed.
The characteristics required for the recording sheet for ink jet recording are generally (1) fast drying (high ink absorption speed), and (2) ink dot diameter is appropriate and uniform. (No blurring), (3) good graininess, (4) high dot roundness, (5) high color density, (6) high chroma (dullness) (7) The light resistance, gas resistance and water resistance of the printed portion are good, (8) the whiteness of the recording sheet is high, and (9) the preservability of the recording sheet is good ( (No long-term storage, yellowing coloration, long-term storage does not cause image blur), (10) Stable deformation, good dimensional stability (curl is sufficiently small), (11) Hard running performance Is good. In addition to the above properties, glossy, surface smoothness, photographic paper-like texture similar to silver salt photography, etc. can be used for photo glossy paper used for the purpose of obtaining so-called photo-like high-quality recorded matter. Required. In particular, the ink absorptivity is required to have a higher level by improving the head.

On the other hand, image receiving paper containing colloidal silica has been proposed for the purpose of improving glossiness and ink absorbability (see, for example, Patent Documents 1 and 2), but it corresponds to high-speed printing / associative ink. There are still challenges.
A recording medium containing a specific polymer has been proposed for the purpose of increasing the concentration, suppressing bleeding, and improving ozone resistance (see, for example, Patent Document 3), and further improvement of the surface shape is desired. It is rare.

Furthermore, an ink jet recording method using a specific highly associative ink has been proposed for the purpose of improving ink storage stability, clogging recovery, and high fastness (for example, see Patent Document 4). Suppression is desired.
JP 2003-159862 A JP 2004-50811 A JP 2006-241416 A JP 2004-2670 A

  The present invention has been made in view of the above problems, and the object thereof is also in the case of using an ink having an excellent surface shape and excellent ink absorbability and containing a highly associative dye. Another object of the present invention is to provide an ink jet recording medium that suppresses the generation of bronzes, a method for producing the same, and an ink jet recording method that uses the ink jet recording medium.

Means for solving the above-mentioned problems are as follows.
That is, the present invention
<1> A peak obtained when the ink receiving layer is collected on the support, the ink receiving layer is collected, and the collected ink receiving layer is measured by solid ¹¹ B-NMR is represented by the following formula (1). The defined A is 0.6 or less, and the ink receiving layer includes at least a step of applying a coating liquid containing a boron compound to form a coating layer on a support, and the coating layer, An inkjet recording medium, wherein the coating layer formed by applying the coating solution is formed through a step of applying a basic solution having a pH of 7.1 or higher after decreasing drying.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm)

<2> A support having an ink receiving layer and a gloss developing layer on the support, collecting the ink receiving layer and the gloss developing layer, and mixing the collected ink receiving layer and the gloss developing layer as a solid ¹¹ B- The peak obtained by NMR measurement is that A defined by the following formula (1) is 0.6 or less, and the ink receiving layer is coated with a coating liquid containing at least a boron compound. A step of forming a coating layer thereon, and a step of applying a basic solution having a pH of 7.1 or more after the coating layer formed by coating the coating solution on the coating layer exhibits reduced-rate drying. An ink jet recording medium characterized by being formed through the process.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm)

<3> The ink jet recording medium according to <1> or <2>, wherein the ink receiving layer contains a compound containing a thioether group or a sulfoxide compound.
<4> The ink receiving layer contains a water-soluble resin and inorganic fine particles in a ratio of 0.23 to 0.33 parts by mass of the water-soluble resin with respect to 1 part by mass of the inorganic fine particles. The inkjet recording medium according to any one of 1> to <3>.

<5> An ink receiving layer is provided on a support, the ink receiving layer is sampled, and a peak obtained when the collected ink receiving layer is measured by solid ¹¹ B-NMR is defined by the following formula (1). A step of forming a coating layer by applying a coating liquid containing a boron compound on a support at least to an ink receiving layer of an inkjet recording medium having A of 0.6 or less; and The coating layer formed by applying the coating solution has a step of forming on the support through a step of applying a basic solution having a pH of 7.1 or higher after the coating layer exhibits reduced-rate drying. This is a method for manufacturing an inkjet recording medium.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm)

<6> A sample having an ink receiving layer and a gloss developing layer on a support, collecting the ink receiving layer and the gloss developing layer, and mixing the collected ink receiving layer and the gloss developing layer is obtained by solid ¹¹ B-NMR. The peak obtained when measured is the ink receiving layer of the ink jet recording medium defined by the following formula (1) having an A of 0.6 or less, and at least a coating liquid containing a boron compound on the support. A step of coating to form a coating layer, and a step of applying a basic solution having a pH of 7.1 or higher after the coating layer formed by coating the coating solution on the coating layer exhibits reduced-rate drying And a method of producing an ink jet recording medium, comprising a step of forming the support on a support.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm)

<7> An image is recorded by ejecting ink containing a dye represented by the following general formula (I) onto the ink jet recording medium according to any one of <1> to <4>. This is an ink jet recording method.

(In the general formula (I), M represents a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. Pc represents a (k + l + m + n) -valent phthalocyanine nucleus represented by the following general formula (II). X ₁ , X ₂ , X ₃ , and X ₄ each independently represent —SO—R ₁ , —SO ₂ —R ₁ , —SO ₂ NR ₂ R ₃ , —CONR ₂ R ₃ , —CO ₂ —. R ₁ or CO—R ₁ is present, and at least one each exists in each of the four benzene rings {A, B, C, D in the general formula (II) in the phthalocyanine nucleus, provided that X is X _{1, X 2,} X 3, _{X 4} are not be all the same, _and, .R ₁ having as X _1, X _2, X 3, at least one substituent an ionic hydrophilic group _{X 4} Is a substituted or unsubstituted alkyl group, substituted or R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₃ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, k represents an integer of 0 <k <8, and l represents 0 <l <8 M represents an integer of 0 ≦ m <8, and n represents an integer of 0 ≦ n <8, where k, l, m, and n represent numbers satisfying 4 ≦ k + 1 + m + n ≦ 8. ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ each independently represents a hydrogen atom or a monovalent substituent, each monovalent substituent further comprising a substituent. (You may have it.)

  According to the present invention, an ink jet recording medium having an excellent surface shape, excellent ink absorbability, and suppressing the occurrence of bronzing even when using an ink containing a highly associative dye, and a method for producing the same In addition, an ink jet recording method using the ink jet recording medium can be provided.

<Inkjet recording medium>
The ink jet recording medium according to the first aspect of the present invention has an ink receiving layer on a support, the ink receiving layer is collected, and the collected ink receiving layer is measured by solid-state ¹¹ B-NMR measurement. A peak defined by the following formula (1) is 0.6 or less, and the ink receiving layer forms a coating layer on the support by applying a coating liquid containing at least a boron compound. And a step of applying a basic solution having a pH of 7.1 or higher after the coating layer formed by applying the coating solution to the coating layer exhibits reduced-rate drying. Preferably, the coating layer is crosslinked and cured by a step of applying a basic solution having a pH of 7.1 or higher.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm)

The ink jet recording medium of the second aspect of the present invention has an ink receiving layer and a gloss developing layer on a support, and collecting the ink receiving layer and the gloss developing layer. The peak obtained when solid ¹¹ B-NMR measurement is performed on the sample mixed with the glossy layer is A or less defined by the formula (1) is 0.6 or less, and the ink receiving layer is at least water-soluble. The step of applying a coating solution containing a resin and a boron compound to form a coating layer on a support, and the coating layer formed by coating the coating solution on the coating layer shows reduced-rate drying. After forming a basic solution having a pH of 7.1 or higher, and applying the basic solution having a pH of 7.1 or higher to cross-link and cure the coating layer. preferable.

(Inkjet recording medium of the first aspect)
The ink jet recording medium according to the first aspect of the present invention has an ink receiving layer on a support, the ink receiving layer is collected, and the collected ink receiving layer is measured by solid-state ¹¹ B-NMR measurement. In the peak to be obtained, A defined by the formula (1) is 0.6 or less.
First, the ink jet recording medium according to the first aspect of the present invention will be described.

[Ink receiving layer]
In the ink-receiving layer in the ink jet recording medium of the first aspect of the present invention, the peak obtained when the sample sampled as described above is measured by solid ¹¹ B-NMR is A defined by the above formula (1). It is 0.6 or less. Here, the peak area obtained when the solid ¹¹ B-NMR measurement is performed is proportional to the amount of boron in the sample. The peak area in the range of 5 to 10 ppm is mainly proportional to the amount of tricoordinate boron, and the peak area in the range of -5 to 5 ppm is mainly proportional to the amount of tetracoordinate boron.

Here, the collection of the ink-receiving layer, and the solid ^{11 B-NMR} measurement of the ink-receiving layer collected is scraped ink receiving layer on the support of the ink jet recording medium, which was measured solid ^{11 B-NMR} under the following conditions It is.
Apparatus: AVANCE 300 and 7 mm manufactured by Bruker o. d. BL probe and measurement conditions MAS rotation speed: 5 kHz
・¹¹ B observation pulse width: 2.0μs
Repeat time: 2 sec
Integration count: 2048 Observation width: 150 kHz
Chemical shift standard: H ₃ BO ₃ 19.49 ppm

[Boron compounds]
The ink receiving layer in the ink jet recording medium of the first aspect of the present invention contains a boron compound for crosslinking an organic binder described later. By containing the boron compound, a three-dimensional network structure cured by a crosslinking reaction between the boron compound and the organic binder is formed, and a translucent porous film can be formed.
Furthermore, as a result of intensive studies, the present inventors have determined that when the boron compound used for crosslinking the organic binder in the ink-receiving layer is a tetracoordinate boron compound, the crosslinking of the organic binder proceeds, and the formula When A defined in (1) is 0.6 or less (the amount of tetracoordinate boron compound in the boron compound to be used is a certain amount or more), the ink absorbability is excellent and the high associative property is high. It has been found that even when an ink containing a dye is used, the occurrence of bronzing can be suppressed.

In the ink jet recording medium of the first aspect of the present invention, A defined by the formula (1) must be 0.6 or less, and is preferably 0.58 or less. When A defined by the above formula (1) exceeds 0.6, the effect of suppressing the occurrence of bronzing is obtained even in the case of using an ink having excellent ink absorptivity and containing a highly associative dye. I can't.
Examples of the method of setting A defined by the formula (1) to 0.6 or less include a method of applying a basic solution having a pH of 7.1 or more when forming the ink receiving layer as described later.

Examples of the boron compound include borax, boric acid, and borate (for example, orthoborate, InBO ₃ , ScBO ₃ , YBO ₃ , LaBO ₃ , Mg ₃ (BO ₃ ) ₂ , Co ₃ (BO ₃ ) ₂ , Diborate (eg, Mg ₂ B ₂ O ₅ , Co ₂ B ₂ O ₅ ), metaborate (eg, LiBO ₂ , Ca (BO ₂ ) ₂ , NaBO ₂ , KBO ₂ ), tetraborate (eg, _{, Na 2 B 4 O 7 ·} 10H 2 O), can be mentioned five borate _{(e.g., KB 5 O 8 · 4H 2} O, Ca 2 B 6 O 11 · 7H 2 O, CsB 5 O 5) , etc. Among them, borax, boric acid, and borate are preferable, and boric acid is particularly preferable in that a crosslinking reaction can be promptly caused.

  1-50 mass% is preferable with respect to the mass of an organic binder, and, as for the usage-amount of a boron compound, 5-40 mass% is more preferable.

[Other cross-linking agents]
Moreover, in the range which does not inhibit the effect of this invention, the following compounds other than a boron compound can also be used as a crosslinking agent. Examples of crosslinking agents other than boron compounds include aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde; ketone compounds such as diacetyl and cyclopentanedione; bis (2-chloroethylurea) -2-hydroxy-4, Active halogen compounds such as 6-dichloro-1,3,5-triazine and 2,4-dichloro-6-S-triazine sodium salt; divinylsulfonic acid, 1,3-vinylsulfonyl-2-propanol, N, N Active vinyl compounds such as' -ethylenebis (vinylsulfonylacetamide) and 1,3,5-triacryloyl-hexahydro-S-triazine; N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin; melamine resin ( For example, methylol melamine, alkylated methylol Melamine); epoxy resin;

Isocyanate compounds such as 1,6-hexamethylene diisocyanate; Aziridine compounds described in US Pat. Nos. 3,017,280 and 2,983,611; Carboximide compounds described in US Pat. No. 3,100,704; Glycerol triglycidyl Epoxy compounds such as ether; Ethyleneimino compounds such as 1,6-hexamethylene-N, N′-bisethyleneurea; Halogenated carboxaldehyde compounds such as mucochloric acid and mucophenoxycyclolic acid; 2,3-dihydroxy Dioxane compounds such as dioxane; Titanium lactate, aluminum sulfate, chromium alum, potash alum, metal-containing compounds such as zirconyl acetate and chromium acetate, polyamine compounds such as tetraethylenepentamine, and hydrazide compounds such as adipic acid dihydrazide It is a small molecule or polymer or the like containing an oxazoline group two or more. Said crosslinking agent may be used individually by 1 type or in combination of 2 or more types.

The ink receiving layer in the ink jet recording medium of the first aspect of the present invention preferably contains inorganic fine particles. Here, as content of an inorganic fine particle, it is preferable to contain 40-85 mass% with respect to the total solid which comprises an ink receiving layer, and it is preferable to contain 50-75 mass%. Further, the total amount of the inorganic fine particles contained in the ink receiving layer (meaning that the total amount when there are two or more ink receiving layers containing inorganic fine particles) is 10 to 25 g / m ^2. Preferably, the range of 12-20 g / m ² is more preferable.

The kind of inorganic fine particles used in the ink jet recording medium of the first aspect of the present invention is not particularly limited, but gas phase method silica, alumina, or alumina hydrate is preferable in terms of gloss and ink absorbability. These inorganic fine particles may be used alone or in combination.
In the ink jet recording medium according to the first aspect of the present invention, the ink receiving layer may have a single-layer structure or a multi-layer structure. In the case of a one-layer structure, for example, there is an aspect in which one kind of vapor phase method silica, alumina, and alumina hydrate is contained alone, or an aspect in which a plurality of kinds are used in combination.
When the ink receiving layer has a plurality of layers, there are, for example, a mode in which a plurality of layers are formed by only one kind of gas phase method silica, alumina, and alumina hydrate, a mode in which different types are contained in separate layers, and the like. However, specific examples include a two-layer configuration of a vapor-phase method silica-containing layer and a layer containing alumina or alumina hydrate, or an embodiment in which vapor-phase method silica having different particle diameters is contained in separate layers. It is done.

  Vapor phase silica preferably used in the present invention is also called a dry method as opposed to a wet method, and is generally made by a flame hydrolysis method. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane can be used alone or silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state. Vapor phase method silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd., and can be obtained.

The average primary particle diameter of the vapor phase silica is preferably 5 to 50 nm, and in order to obtain higher gloss, it is preferable to use a silica having a specific surface area of 5 to ²⁰ nm and a BET method of 90 to 400 m ² / g. . The BET method referred to in the present invention is one of powder surface area measurement methods by vapor phase adsorption, and is a method for determining the total surface area, that is, the specific surface area of a 1 g sample from the adsorption isotherm. Usually, nitrogen gas is often used as the adsorbed gas, and the most frequently used method is to measure the amount of adsorption from the change in pressure or volume of the gas to be adsorbed. The most prominent expression for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, and Teller equation, called the BET equation, which is widely used for determining the surface area. The adsorption amount is obtained based on the BET equation, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.

  As the alumina used in the present invention, γ-alumina which is a γ-type crystal of aluminum oxide is preferable, and among them, a δ group crystal is preferable. Although γ-alumina can reduce the primary particles to about 10 nm, usually, secondary particles of several thousand to several tens of thousands of nanometers are mixed with ultrasonic waves, high-pressure homogenizers, counter-impact type jet crushers, etc. What grind | pulverized to about 300 nm can be used preferably.

The alumina hydrate used in the present invention is represented by a constitutional formula of Al ₂ O ₃ .nH ₂ O (n = 1 to 3). The case where n is 1 represents an alumina hydrate having a boehmite structure, and the case where n is greater than 1 and less than 3 represents an alumina hydrate having a pseudo boehmite structure. It can be obtained by a known production method such as hydrolysis of an aluminum alkoxide such as aluminum isopropoxide, neutralization of an aluminum salt with an alkali, or hydrolysis of an aluminate.

  The average particle size of the primary particles of alumina hydrate is preferably 5 to 50 nm, and in order to obtain higher gloss, it is 5 to 20 nm and the average aspect ratio (ratio of average particle size to average thickness) is 2 or more. It is preferable to use the tabular grains.

  In the present invention, the ink receiving layer preferably contains an organic binder in order to maintain the properties as a film. As the organic binder, various water-soluble resins or polymer latexes are preferably used. As the water-soluble resin, for example, polyvinyl alcohol, polyethylene glycol, starch, dextrin, carboxymethyl cellulose, polyvinyl pyrrolidone, polyacrylic acid ester and the like and derivatives thereof are used. Particularly preferred organic binders are completely or partially saponified. Polyvinyl alcohol or cation-modified polyvinyl alcohol.

  Particularly preferred among the polyvinyl alcohols are those having a degree of saponification of 80% or more or those completely saponified. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferred. The cation-modified polyvinyl alcohol has a primary to tertiary amino group or a quaternary ammonium group in the main chain or side chain of the polyvinyl alcohol as described in, for example, JP-A-61-10383. Polyvinyl alcohol.

  Examples of the polymer latex used as the organic binder include acrylic latexes such as alkyl ester, aryl group, aralkyl group, and hydroxyalkyl group, such as acrylic ester or methacrylic ester, acrylonitrile, acrylamide, acrylic acid. And methacrylic acid or other homopolymers or copolymers, or the above monomers and styrene sulfonic acid, vinyl sulfonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, vinyl isocyanate, allyl isocyanate, vinyl methyl ether, acetic acid Examples thereof include copolymers with vinyl, styrene, divinylbenzene and the like. As the olefin latex, a polymer comprising a copolymer of a vinyl monomer and a diolefin is preferable. As the vinyl monomer, styrene, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, or the like is preferably used. Examples include butadiene, isoprene, chloroprene and the like.

  In the ink-receiving layer in the ink jet recording medium of the first aspect of the present invention, it is preferable to use an organic binder in the range of 5 to 35% by mass, particularly 10 to 30% by mass, based on the inorganic fine particles. Is preferred.

  The ink receiving layer in the ink jet recording medium of the first aspect of the present invention preferably contains inorganic fine particles and a water-soluble resin as an organic binder, and the water-soluble resin and the inorganic fine particles contain 1 mass of inorganic fine particles. It is more preferable to contain in the ratio of 0.23-0.33 mass part of water-soluble resin with respect to a part, The ratio of 0.23-0.33 mass part of water-soluble resin with respect to 1 mass part of inorganic fine particles It is further preferable to contain. When the water-soluble resin and the inorganic fine particles are contained in a ratio of 0.23 to 0.33 parts by mass of the water-soluble resin with respect to 1 part by mass of the inorganic fine particles, it is easy to form a porous film that is not film-like. .

  In the ink jet recording medium of the first aspect of the present invention, when the ink-receiving layer contains vapor phase method silica as inorganic fine particles, it is preferable that a cationic compound is also contained. By containing a cationic compound in the ink receiving layer, cracking of the ink receiving layer can be prevented and water resistance can be improved.

  As the cationic compound used in the ink jet recording medium of the first aspect of the present invention, a cationic polymer or a water-soluble polyvalent metal compound is preferably used. These cationic compounds and water-soluble polyvalent metal compounds can be used alone or in combination.

Examples of the cationic polymer include water-soluble cationic polymers having a quaternary ammonium group, a phosphonium group, or an acid adduct of a primary to tertiary amine. For example, polyethylenimine, polydialkyldiallylamine, polyallylamine, allylamine epichlorohydrin polycondensate, JP-A 59-20696, 59-33176, 59-33177, 59-1555088, 60-11389 60-49990, 60-83882, 60-109894, 62-198493, 63-49478, 63-115780, 63-280681, JP-A-1-40371, Examples thereof include cationic polymers described in JP-A-6-234268, JP-A-7-125411, JP-A-10-193976, and the like. The weight average molecular weight of the cationic polymer used in the present invention is preferably 100,000 or less, more preferably 50,000 or less, and the lower limit is about 2,000.
The amount of these cationic polymers used is preferably in the range of 1 to 10% by weight with respect to the inorganic fine particles.

  Examples of the polyvalent metal in the water-soluble polyvalent metal compound include calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, titanium, chromium, magnesium, tungsten, and molybdenum. It can be used as a water-soluble metal salt. 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 copper (II) chloride dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel sulfate Ammonium hexahydrate, nickel amidosulfate tetrahydrate, aluminum sulfate, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferric chloride Ferrous, ferric chloride, ferrous sulfate, ferric sulfate, zinc bromide, zinc chloride, zinc nitrate Hydrate, zinc sulfate, zirconium acetate, zirconium nitrate, basic zirconium carbonate, zirconium hydroxide, zirconium carbonate / ammonium, zirconium carbonate / potassium, zirconium sulfate, zirconium fluoride, zirconium chloride, zirconium chloride octahydrate, oxy Zirconium chloride, hydroxy zirconium chloride, titanium chloride, titanium sulfate, chromium acetate, chromium sulfate, magnesium sulfate, magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, sodium tungsten citrate, 12 tungstorin Examples include acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n hydrate, and the like. Among these, aluminum or a water-soluble salt of a periodic table group IVa element (zirconium, titanium) is preferable. In the present invention, water-soluble means that 1% by mass or more dissolves in water at room temperature and normal pressure.

As a water-soluble aluminum compound other than the above, a basic polyaluminum hydroxide compound is preferably used. The basic polyaluminum hydroxide compound has a main component represented by the following general formula (A). For example, [Al ₂ (OH) ₅ ] Cl, [Al ₂ (OH) _4.5 ] Cl _1.5 , [Al ₂ ( OH) ₄ ] Cl _{2 and} other water-soluble polyaluminum hydroxides. In addition, the basic polyaluminum hydroxide compound becomes a very complicated system in an aqueous solution, and includes a high polymer, a low polymer, a dimer, and a monomer. In the general formula (A), n and m represent a numerical value of 0 or more and less than 6.
_{[Al 2 (OH) n Cl} 6-n] m ·· general formula (A)

  The basic polyaluminum hydroxide compound is a water treatment agent in the name of polyaluminum chloride (PAC) from Taki Chemical Co., Ltd., and the name of polyaluminum hydroxide (Paho) in Asada Chemical Co., Ltd. It is commercially available from Riken Green under the name Purachem WT and from other manufacturers for the same purpose, and various grades are readily available. In the present invention, these commercially available products can be used as they are. These basic polyaluminum hydroxide compounds are also described in Japanese Patent Publication Nos. 3-24907 and 3-42591.

In the ink jet recording medium of the first aspect of the present invention, the content of the water-soluble polyvalent metal compound in the ink receiving layer is 0.1 g / m ^{2 to} 10 g / m ² , preferably 0.2 g / m. m ^{2 to 5} g / m ² .

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

  In the ink jet recording medium of the first aspect of the present invention, the ink receiving layer preferably contains a hardener together with an organic binder. Specific examples of the hardener 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, N-methylol compounds as described in Japanese Patent No. 2,732,316, isocyanates as described in US Pat. No. 3,103,437, US Pat. Nos. 3,017,280 and 2,983,611 described Aziridines such as carbodiimide compounds as described in US Pat. No. 3,100,704, There are epoxy compounds as described in No. 3,091,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, boric acid and inorganic hardeners such as borate, These can be used alone or in combination of two or more. Among these, boric acid or borate is particularly preferable. The addition amount of the hardener is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass with respect to the hydrophilic binder constituting the ink receiving layer.

  The ink receiving layer in the ink jet recording medium of the first aspect of the present invention preferably contains a compound containing a sulfur atom. A compound containing a sulfur atom is a compound that itself can be oxidized, and when added to the ink receiving layer, plays a role of improving the ozone resistance of the ink receiving layer. Preferred examples of the compound containing a sulfur atom include compounds containing a thioether group and sulfoxide compounds.

-Compound containing a thioether group-
Specific examples of the compound containing a thioether group according to the present invention (Exemplary Compounds A-1 to A-77) are shown below, but the present invention is not limited thereto.

The content in the ink receiving layer of a compound containing the thioether group is preferably from 0.1 to 50 mmol / ^{m 2} is more preferably 0.2 to 20 mmol / ^{m 2.}

-Sulphoxide compounds-
The sulfoxide compound according to the present invention is not particularly limited, but preferably has at least one structure represented by the following general formula (1) in the molecule.

  The sulfoxide compound having the structure represented by the general formula (1) may be substituted with a hydrophilic group. Hydrophilic groups include substituted or unsubstituted amino groups, substituted or unsubstituted carbamoyl groups, substituted or unsubstituted sulfamoyl groups, substituted or unsubstituted ammonium, hydroxyl groups, sulfonic acids, carboxylic acids, phosphoric acids, ethylene Examples thereof include oxyacids and substituted or unsubstituted nitrogen-containing heterocycles.

  Furthermore, the sulfoxide compound is preferably a compound represented by the following general formula (2).

［一般式（２）中、Ｒ^１及びＲ^３は、それぞれ独立に、置換又は無置換のアルキル基、置換又は無置換のアリール基、置換又は無置換のヘテロ環基、又はそれらからなるポリマー残基を表し、Ｒ^１とＲ^３は同一でも異なってもよく、結合して環を形成していてもよい。Ｒ^２は、置換又は無置換の２〜６価の連結基を表し、Ｒ^１及びＲ^２、Ｒ^２及びＲ^３と結合して環を形成していてもよい。ｍは０又は１以上の整数を表し、ｎは０又は１を表す。Ｒ^１、Ｒ^２、及びＲ^３のうちの少なくともいずれかは、置換又は無置換のアミノ基、置換又は無置換のカルバモイル基、置換又は無置換のスルファモイル基、置換又は無置換のアンモニウム、ヒドロキシル基、スルホン酸、カルボン酸、リン酸、エチレンオキシ基、置換又は無置換の含窒素へテロ環で表される親水性基で置換されたアルキル基、アリール基、ヘテロ環基、及びポリマー残基を表す。］

[In General Formula (2), each of R ¹ and R ³ independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a polymer residue composed thereof. Represents a group, and R ¹ and R ³ may be the same or different, and may combine to form a ring. R ² represents a substituted or unsubstituted divalent to hexavalent linking group, and may be bonded to R ¹ and R ² , R ² and R ³ to form a ring. m represents 0 or an integer of 1 or more, and n represents 0 or 1. At least one of R ¹ , R ² , and R ³ is a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted ammonium, or a hydroxyl group Sulfonic acid, carboxylic acid, phosphoric acid, ethyleneoxy group, alkyl group substituted with a hydrophilic group represented by a substituted or unsubstituted nitrogen-containing heterocycle, aryl group, heterocyclic group, and polymer residue To express. ]

In the general formula (2), the unsubstituted alkyl group represented by R ¹ and R ³ may be a linear, branched, or cyclic structure, and may have an unsaturated bond. An alkyl group having 1 to 22 is preferable, and specifically, methyl group, ethyl group, allyl group, n-butyl group, n-hexyl group, n-octyl group, benzyl group, iso-propyl group, iso-butyl. Group, sec-butyl group, cyclohexyl group, 2-ethylhexyl group and the like. Among them, an alkyl group having 1 to 10 carbon atoms is more preferable, methyl group, ethyl group, allyl group, n-propyl group, iso-butyl. Group, cyclohexyl group and 2-ethylhexyl group are particularly preferred.

As the unsubstituted aryl group represented by R ¹ and R ^3, for example, preferably an aryl group having 6 to 22 carbon atoms, specifically, a phenyl group, 1-naphthyl, 2-naphthyl and the like Among them, a phenyl group is particularly preferable.

Examples of the unsubstituted heterocyclic group represented by R ¹ and R ³ include thienyl group, thiazolyl group, oxazolyl group, pyridyl group, pyrazyl group, thiadiazoyl group, triazoyl group, morpholyl group, piperazyl group, pyrimidyl group, triazyl group Group, indolyl group, benzothiazoyl group, benzoxazoyl group, among which thiazolyl group, oxazoyl group, pyridyl group, thiadiazoyl group, triazoyl group, morpholyl group, pyrimidyl group, triazyl group, benzothiazoyl group, benzo Oxazoyl groups are particularly preferred.

When R ¹ and R ³ represent a polymer residue comprising a substituted or unsubstituted alkyl group, aryl group, or heterocyclic residue, examples of the polymer residue include polymers having the following units.

［Ｒ^４は、水素原子、又は炭素数１〜４のアルキル基を表し、Ｒ^５はアルキレン基を表し、Ｑは連結基を表す。Ｒ^７、Ｒ^８はアルキレン基を表し、Ｌは１又は２を表し、Ｐは１又は２を表す。Ｒ^２、Ｒ^３、ｍ、ｎは、スルホキシド系化合物として好ましい前記一般式（２）中のＲ^２、Ｒ^３、ｍ、ｎと同義である］

[R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ represents an alkylene group, and Q represents a linking group. R ⁷ and R ⁸ represent an alkylene group, L represents 1 or 2, and P represents 1 or 2. ^{R 2, R 3, m,} n are, ^{R 2,} R 3 in the preferred general formula as the sulfoxide-based compound (2), m, is synonymous with n]

  Examples of the linking group represented by Q in the unit include the following linking groups.

［Ｒ^６は水素原子、アルキル基、アリール基を表す。］

[R ⁶ represents a hydrogen atom, an alkyl group, or an aryl group. ]

When R ¹ and R ³ represent an alkyl group, an aryl group, or a heterocyclic residue, the substituent is a substituted or unsubstituted amino group (for example, an amino group having 30 or less carbon atoms, an amino group, an alkylamino group). , Dialkylamino group, arylamino group, acylamino group), substituted or unsubstituted carbamoyl group (for example, carbamoyl group having 30 or less carbon atoms, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group) Group), substituted or unsubstituted ammonium (for example, ammonium having 30 or less carbon atoms, ammonium, trimethylammonium, triethylammonium, dimethylbenzylammonium, hydroxyethyldimethylammonium), substituted or unsubstituted sulfamoyl group (for example, 3 carbon atoms) The following sulfamoyl group, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, morpholinosulfamoyl group, piperidinosulfamoyl group), substituted or unsubstituted nitrogen-containing heterocycle (for example, pyridyl group, A hydrophilic group represented by a pyrimidyl group, morpholino group, pyrrolidino group, piperidino group, piperazyl group), hydroxyl group, sulfonic acid, carboxylic acid, phosphoric acid, ethyleneoxy group, cyano group, halogen atom (for example, fluorine atom) , Chlorine atom, bromine atom), substituted or unsubstituted alkoxycarbonyl group (for example, alkoxycarbonyl group having 30 or less carbon atoms, methoxycarbonyl group, ethoxycarbonyl group, dimethylaminoethoxyethoxycarbonyl group, diethylaminoethoxycarbonyl group, hydroxyethoxy) Carbonyl Group), a substituted or unsubstituted aryloxycarbonyl group (for example, an aryloxycarbonyl group having 30 or less carbon atoms, a phenoxycarbonyl group), a substituted or unsubstituted alkoxy group (for example, an alkoxy group having 30 or less carbon atoms, a methoxy group) , Ethoxy group, phenoxyethoxy group, butoxyethoxy group, hydroxyethoxy group), substituted or unsubstituted aryloxy group (for example, aryloxy group having 30 or less carbon atoms, phenoxy group), substituted or unsubstituted acyloxy group (for example, , An acyloxy group having 30 or less carbon atoms, an acetyloxy group, a propionyloxy group), a substituted or unsubstituted acyl group (for example, an acyl group having 30 or less carbon atoms, an acetyl group, or a propionyl group).
R ¹ and R ³ may be the same or different, and may be combined to form a ring.

R ² represents a substituted or unsubstituted divalent to hexavalent linking group, and may combine with R ¹ and R ² , R ² and R ³ to form a ring. Examples of the sulfur-containing heterocycle formed by combining R ¹ , R ² , and R ³ with each other include thienyl group, thiazoyl group, thiazolidyl group, dithiolan-2-yl group, trithian-2-yl group, and dithian-2-yl group. , Etc.

The divalent to hexavalent linking group represented by R ² is a linking group containing carbon, nitrogen, oxygen, and phosphorus, and specifically includes the following linking groups.

  These linking groups may contain a hetero bond such as an ether bond, an ester bond, an amino bond, an amide bond, or a urethane bond, and may further have a substituent. Moreover, the polymer in which those connection groups are repeated may be sufficient. In that case, the linking groups may be the same or different.

At least one of R ¹ , R ² , and R ³ is a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted ammonium, a hydroxyl group, a sulfone It represents an alkyl group, an aryl group, a heterocyclic group, and a polymer residue substituted with an acid, a carboxylic acid, a phosphoric acid, an ethyleneoxy group, a hydrophilic group represented by a substituted or unsubstituted nitrogen-containing heterocyclic ring. Examples of these hydrophilic groups include the substituents described in the above R ¹ and R ³ .

Since the ink jet recording medium of the present invention is substantially applied by aqueous coating, the sulfoxide compound according to the present invention is preferably water-soluble.
Further, the sulfoxide compound is a Lewis base, has higher water solubility than a thioether compound, and can be added in a larger amount.

When the sulfoxide compound according to the present invention is water-soluble, it is preferably added to a coating solution or a basic solution containing fine particles and a water-soluble resin described later.
Further, when the sulfoxide compound according to the present invention is oil-soluble, it is preferably added to an application solution or a basic solution containing fine particles and a water-soluble resin by adding as an emulsified dispersion or an organic solvent. .

In the inkjet recording medium of the present invention, the content of the sulfoxide compound is 0.01 to 20 g / m ² in order to further improve ozone resistance, aging blur (image blur), and glossiness. Preferably, it is 0.05-7 g / m < ² >.

  In the inkjet recording medium of the present invention, the sulfoxide-based compound generally has a higher oxidation potential than conventional sulfur-containing compounds (thioethers, thioureas), and is more advantageous for the purpose of improving ozone resistance and light resistance. By combining with a dye having a high oxidation potential, higher ozone resistance and light resistance can be expressed.

  The sulfoxide compounds according to the present invention may be used alone or in combination of two or more.

  Specific examples (Exemplary Compounds A-1 to A-75) of the sulfoxide-based compound are shown below, but the present invention is not limited thereto.

The content in the ink receiving layer of a compound containing more sulfur atoms is preferably in a 0.01 to 20 g / ^{m 2,} and more preferably a 0.05~7g / ^{m 2.}

  For the ink receiving layer, coloring dyes, coloring pigments, ink dye fixing agents, UV absorbers, antioxidants, pigment dispersants, antifoaming agents, leveling agents, preservatives, fluorescent whitening agents, viscosity stabilizers Various known additives such as a pH adjuster can also be added.

  In the ink jet recording medium of the first aspect of the present invention, the thickness of the ink receiving layer is preferably 5 to 50 μm, more preferably 15 to 40 μm. Here, when there are a plurality of ink receiving layers, the film thickness of the ink receiving layer refers to the total thickness of the plurality of ink receiving layers.

The ink receiving layer in the ink jet recording medium according to the first aspect of the present invention includes a step of applying a coating liquid containing at least a boron compound to form a coating layer on a support, and the coating layer, The coating layer formed by applying the coating solution is formed through a step of applying a basic solution having a pH of 7.1 or more and performing cross-linking and curing of the coating layer after exhibiting reduced-rate drying. And That is, the ink jet recording medium of the first aspect of the present invention has an ink receiving layer on a support, and the ink receiving layer is coated with at least a coating liquid containing a boron compound on the support. After the step of forming a coating layer, and after the coating layer formed by coating the coating solution on the coating layer shows reduced-rate drying, a step of applying a basic solution having a pH of 7.1 or more, The peak obtained when the ink-receiving layer is collected and the collected ink-receiving layer is measured by solid-state ¹¹ B-NMR is obtained by the above formula ( A defined in 1) is 0.6 or less.

  When the ink receiving layer is formed as described above, A defined by the above formula (1) can be reduced to 0.6 or less by applying a basic solution having a pH of 7.1 or higher. In addition, after the coating layer formed by applying the coating solution shows reduced-rate drying, an ink receiving layer in which the coating layer is crosslinked and cured is formed by applying a basic solution having a pH of 7.1 or more. An ink jet recording medium having an excellent surface shape can be obtained.

  Here, “after the coating layer exhibits reduced-rate drying” usually refers to after several minutes have passed since the coating solution for the ink receiving layer was applied. Before showing reduced-rate drying, the content of the solvent (dispersion medium) in the applied coating layer shows a phenomenon of “constant-rate drying” in which it decreases in proportion to time, and after showing reduced-rate drying The solvent in the coating layer is almost evaporated. About the time which shows this "constant rate drying", it describes in chemical engineering handbook (pages 707-712, Maruzen Co., Ltd. issue, October 25, 1980), for example.

  The ink receiving layer in the ink jet recording medium of the first aspect of the present invention is formed as follows, for example. A coating solution for forming an ink receiving layer containing at least gas phase method silica, a water-soluble resin (for example, PVA), and a boron compound is used as gas phase method silica and PVA aqueous solution (for example, about 15% of the above gas phase method silica). For example, 2000 rpm (preferably 1000 rpm) with a high speed rotating homomixer (for example, trade name “T, K homomixer” manufactured by Tokushu Kika Co., Ltd.). It can be prepared by dispersing for 20 minutes (preferably 10 to 30 minutes), for example, under the condition of high speed rotation (˜5000 rpm). The obtained coating liquid is in a uniform sol state, and a porous ink-receiving layer can be formed by coating the coating liquid on a support by a coating method described later and drying it.

  The coating liquid for forming the ink-receiving layer can be made into an aqueous dispersion having an average particle diameter of 10 to 120 nm by making fine particles using a disperser. As the disperser used for obtaining the aqueous dispersion, various conventionally known dispersers such as a disperser can be used. From the viewpoint of efficiently dispersing the formed fine particles, the medium is used. Agitation type dispersers, colloid mill dispersers or high pressure dispersers are preferred

  Moreover, water, an organic solvent, or these mixed solvents can be used for the solvent used for preparation of each liquid. Examples of the organic solvent that can be used for coating include alcohols such as methanol, ethanol, n-propanol, i-propanol, and methoxypropanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, acetonitrile, ethyl acetate, and toluene. .

  In the present invention, the coating method of the coating solution is not particularly limited, and a known coating method can be used. For example, it can be performed by a known coating method such as an extrusion die coater, an air doctor coater, a bread coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, or a bar coater.

  The basic solution (solution B) having a pH of 7.1 or higher can be applied after application of the ink-receiving layer coating solution (coating solution A), but the application is performed after the coating layer exhibits reduced-rate drying. . That is, after the coating liquid A is applied, the coating layer is preferably manufactured by introducing the solution B after the coating layer exhibits a constant rate of drying.

The basic solution (solution B) having a pH of 7.1 or higher can contain a crosslinking agent or the like as necessary. The pH of the basic solution is 7.1 or higher, preferably 7.5 or higher, more preferably 8.0 or higher. If the pH is less than 7.1, the crosslinking reaction of the water-soluble polymer contained in the coating liquid A is not sufficiently performed by the crosslinking agent, and defects such as cracks occur in the ink receiving layer.
The basic solution includes at least a basic substance (for example, ammonia, primary amines (ethylamine, polyallylamine, etc.), secondary amines (dimethylamine, triethylamine, etc.), tertiary amines (N-ethyl-N -Methylbutylamine, etc.), alkali metal or alkaline earth metal hydroxides) and / or salts of the basic substances.

  The basic solution is, for example, adding mordant (basic compound) ammonium carbonate (for example, 1 to 10%) and zirconyl ammonium carbonate (for example, 0.5 to 7%) to ion-exchanged water, It can be prepared with sufficient agitation. In addition, all "%" of each composition means the mass% of a solid part.

  As described above, after the ink-receiving layer coating solution is applied, the coating layer is dried until the coating layer exhibits reduced-rate drying. This drying is generally performed at 40 to 180 ° C. for 0.5 to 10 minutes (preferably 0.5 to 5 minutes). The drying time naturally varies depending on the coating amount, but usually the above range is appropriate.

  As a method for applying the basic solution after the coating layer exhibits reduced drying, (1) a method of further applying the solution B on the coating layer, (2) a method of spraying by a method such as spraying, ( 3) A method of immersing the support having the coating layer formed in the solution B, and the like.

  In the method (1), the application method for applying the solution B includes, for example, curtain flow coater, extrusion die coater, air doctor coater, bread coater, rod coater, knife coater, squeeze coater, reverse roll coater, bar coater. A known coating method such as the above can be used. However, it is preferable to use a method in which the coater does not directly contact an already formed coating layer, such as an extrusion die coater, a curtain flow coater, a bar coater or the like.

  After the application of the basic solution (solution B), it is generally heated at 40 to 180 ° C. for 0.5 to 30 minutes to be dried and cured. Especially, it is preferable to heat at 40-150 degreeC for 1 to 20 minutes.

  Examples of the support used in the ink jet recording medium of the first aspect of the present invention include polyester resins such as polyethylene terephthalate, diasate resins, triacetate resins, acrylic resins, polycarbonate resins, polyvinyl chloride, polyimide resins, cellophane, celluloid and the like. A water-resistant support such as a plastic resin film, a paper and a resin film bonded together, and a polyolefin resin-coated paper in which a hydrophobic resin such as a polyolefin resin is laminated on at least one side of the paper is preferable. These water-resistant supports have a thickness of 50 to 300 μm, preferably 80 to 260 μm.

  The polyolefin resin-coated paper support (hereinafter referred to as polyolefin resin-coated paper) preferably used for the ink jet recording medium of the first aspect of the present invention will be described in detail. The water content of the polyolefin resin-coated paper used in the present invention is not particularly limited, but is preferably in the range of 5.0 to 9.0%, more preferably 6.0 to 9.0% from the curling property. It is a range. The moisture content of the polyolefin resin-coated paper can be measured using any moisture measuring method. For example, an infrared moisture meter, an absolute dry weight method, a dielectric constant method, a Karl Fischer method, or the like can be used.

  The base paper constituting the polyolefin resin-coated paper is not particularly limited, and commonly used paper can be used. However, for example, a smooth base paper used for a photographic support is preferable. As the pulp constituting the base paper, natural pulp, regenerated pulp, synthetic pulp or the like is used alone or in combination. This base paper is blended with additives such as sizing agent, paper strength enhancer, filler, antistatic agent, fluorescent whitening agent, and dye generally used in papermaking.

  Further, a surface sizing agent, surface paper strengthening agent, fluorescent brightening agent, antistatic agent, dye, anchor agent and the like may be applied on the surface.

Further, the thickness of the base paper is not particularly limited, but a paper having good surface smoothness, such as compression by applying pressure with a calendar during paper making or after paper making, is preferable, and its basis weight is 30 to 250 g. / M ² is preferred.

  Examples of the polyolefin resin that coats the base paper include olefin homopolymers such as low density polyethylene, high density polyethylene, polypropylene, polybutene, and polypentene, or copolymers composed of two or more olefins such as ethylene-propylene copolymer, and the like. Of various densities and melt viscosity indices (melt index) can be used alone or as a mixture thereof.

  Further, in the resin of polyolefin resin-coated paper, white pigments such as titanium oxide, zinc oxide, talc, calcium carbonate, fatty acid amides such as stearic acid amide, arachidic acid amide, zinc stearate, calcium stearate, aluminum stearate, 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, manganese purple, etc. It is preferable to add various additives such as magenta pigments and dyes, fluorescent brighteners and ultraviolet absorbers in appropriate combinations.

  As a main method for producing a polyolefin resin-coated paper, it is produced by a so-called extrusion coating method in which a polyolefin resin is cast on a traveling base paper in a heated and melted state, and at least one surface thereof is coated with the resin. Further, before the resin is coated on the base paper, the base paper is preferably subjected to an activation treatment such as corona discharge treatment or flame treatment. From the viewpoint of ink absorption, it is preferable not to cover the surface of the base paper on which the ink receiving layer is provided (the surface of the base paper), and it is preferable to provide a resin layer on the opposite side (the back side of the base paper) from the viewpoint of curling prevention. preferable. The back surface is usually a matte surface, and an active treatment such as corona discharge treatment or flame treatment can be applied to the back surface or both the front and back surfaces as necessary. Moreover, there is no restriction | limiting in particular as thickness of the resin coating layer, but generally resin coating is carried out on the single side | surface or both surfaces by the thickness of 5-50 micrometers on one side. When only one side is coated with a resin, the thickness of the polyolefin resin coating layer is preferably about 5 to 25 μm from the curling property of the resulting ink jet recording medium.

  The surface on which the ink receiving layer of the polyolefin resin-coated paper used in the inkjet recording medium of the first aspect of the present invention is coated (hereinafter referred to as the surface of the polyolefin resin-coated paper) may remain the base paper surface, From the viewpoint of gloss and smoothness, polyolefin resin is heated and melted with an extruder, extruded into a film between a base paper and a cooling roll, pressure-bonded and cooled. At this time, the cooling roll is used to form the surface shape of the polyolefin resin coating layer, and the surface of the resin layer is shaped into a mirror surface, a fine surface, or a patterned silk or mat shape depending on the shape of the cooling roll surface. Can be processed.

  The surface on which the ink receiving layer on the back of the polyolefin resin-coated paper used in the inkjet recording medium of the first aspect of the present invention is coated (hereinafter referred to as the back surface of the polyolefin resin-coated paper) The surface of the base paper may be left as it is, but from the viewpoint of improving curling properties and printed images, it is mainly manufactured by heating and melting polyolefin resin with an extruder, extruding it into a film between the base paper and a cooling roll, pressing and cooling. . At this time, the cooling roll was finely roughened or patterned according to the shape of the surface of the cooling roll so that the Ra specified in JIS-B-0601 was 0.8 to 5 μm from the transportability of the printer and the printed image. For example, it is preferable to mold into a silky shape or a mat shape.

  The method of providing the polyolefin resin coating layer on the back surface or the front surface of the base paper includes a method of irradiating an electron beam after applying an electron beam curable resin, in addition to extruding and applying a heated molten resin, or a coating solution of a polyolefin resin emulsion There is a method of drying after coating and applying a surface smoothing treatment. In any case, a polyolefin resin-coated paper applicable to the present invention can be obtained by molding with a hot roll having irregularities.

An undercoat layer may be provided on the surface of the polyolefin resin-coated paper used in the ink jet recording medium of the first aspect of the present invention. This undercoat layer is applied and dried in advance on the surface of the water-resistant support before the ink receiving layer is applied. The undercoat layer mainly contains a water-soluble polymer or polymer latex that can form a film. Preferred are water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinyl pyrrolidone and water-soluble cellulose, and particularly preferred is gelatin. Adhesion amount of the water-soluble polymer is preferably ^{10~500mg / m 2, 20~300mg / m} 2 is more preferable. Further, the undercoat layer preferably contains a surfactant and a hardener. Further, it is preferable to perform corona discharge before applying the undercoat layer to the resin-coated paper.

(Inkjet recording medium of second aspect)
The ink jet recording medium of the second aspect of the present invention has an ink receiving layer and a gloss developing layer on a support, and the ink receiving layer and the gloss developing layer are collected, and the collected ink receiving layer and gloss developing layer are collected. The peak obtained when a solid ¹¹ B-NMR measurement is performed on a sample in which the layers are mixed has an A defined by the formula (1) of 0.6 or less, and the ink receiving layer includes at least a water-soluble resin and A step of applying a coating solution containing a boron compound to form a coating layer on a support, and after the coating layer formed by coating the coating solution on the coating layer exhibits reduced-rate drying It is characterized by being formed through a step of applying a basic solution having a pH of 7.1 or higher and crosslinking and curing the coating layer.
The ink jet recording medium according to the second aspect of the present invention has a glossy layer, so that it has excellent surface properties and excellent ink absorbability, and also has high gloss.

  The configuration of the ink jet recording medium according to the second aspect of the present invention is not particularly limited, but it is preferable that an ink absorbing layer and a gloss developing layer are provided in this order on a support. Further, other layers may be formed as necessary. When the inkjet recording medium of the second aspect of the present invention has a glossy expression layer, the glossy expression layer is preferably provided as the outermost layer, and an ink absorbing layer and an outermost glossy expression layer on the support are provided. Are more preferably provided in this order so that the ink absorbing layer and the glossy layer are in contact with each other.

The ink receiving layer in the ink jet recording medium of the second aspect of the present invention has a peak obtained when solid ¹¹ B-NMR measurement is performed on a sample obtained by mixing the collected ink receiving layer and glossy expression layer. Except that A defined by is 0.6 or less, the configuration is the same as that of the ink jet recording medium of the first aspect of the present invention described above, and the preferable aspect is also the same. That is, the ink jet recording medium of the second aspect of the present invention has an ink receiving layer and a glossy expression layer on a support, and the ink receiving layer includes at least a boron compound on the support. And a basic solution having a pH of 7.1 or more is applied to the coating layer after the coating layer formed by coating the coating liquid exhibits reduced drying. The ink receiving layer and the gloss developing layer are collected by a manufacturing method having a step of forming on a support through a process, and a sample obtained by mixing the collected ink receiving layer and the gloss developing layer is a solid. ^A peak obtained by ¹¹ B-NMR measurement is such that A defined by the formula (1) is 0.6 or less.
In the inkjet recording medium of the second aspect of the present invention, A defined by the formula (1) must be 0.6 or less as in the inkjet recording medium of the first aspect of the present invention. 0.58 or less is preferable.

  In addition, the ink receiving layer in the ink jet recording medium of the second aspect of the present invention is similar to the ink jet recording medium of the first aspect of the present invention when the ink receiving layer contains vapor phase method silica as inorganic fine particles. In addition, in the ink jet recording medium according to the second aspect of the present invention, a glossy speech layer is further provided on the ink receiving layer containing the cationic compound. As a result, scratch resistance, water resistance, and ink absorbability are further improved, and aggregation at the interface between the two layers is prevented. As a result, uneven coating and uneven gloss are eliminated. When alumina or alumina hydrate is contained as the inorganic fine particles of the ink receiving layer, sufficient cracking and water resistance can be obtained without necessarily using a cationic compound.

  Further, the ink receiving layer in the ink jet recording medium of the second aspect of the present invention is coated with a coating liquid containing at least a boron compound, as in the ink jet recording medium of the first aspect of the present invention. A step of forming a coating layer thereon, and after the coating layer formed by coating the coating solution on the coating layer exhibits reduced-rate drying, a basic solution having a pH of 7.1 or more is applied, It is formed through a step of crosslinking and curing the coating layer.

The coating liquid and the basic solution used for forming the ink receiving layer are the same as the coating liquid and the basic solution in the inkjet recording medium of the first aspect of the present invention.
Further, the pH of the coating solution used for the ink receiving layer in the ink jet recording medium of the second aspect of the present invention is preferably in the range of 3.3 to 6.0, particularly preferably in the range of 3.5 to 5.5. By combining the pH of the ink receiving layer coating solution and the pH 3.3 to 6 of the upper glossy layer coating solution, ink absorbability, glossiness, and a uniform coated surface can be obtained.

  Furthermore, in the ink receiving layer of the ink jet recording medium according to the second aspect of the present invention, a coating solution containing a boron compound is applied to form a coating layer on the support, and a coating solution for the gloss developing layer is further formed. The basic solution may be applied after coating and after the coating solution containing the boron compound exhibits reduced drying.

  The ink jet recording medium according to the second aspect of the present invention further has a gloss developing layer on the ink receiving layer. The glossy layer preferably contains colloidal silica and a cationic compound. This glossy layer is preferably the outermost layer (outermost layer).

  The colloidal silica used in the glossy layer is a colloidal dispersion of silicon dioxide obtained by heating and aging a silica sol obtained through metathesis or acid exchange resin layer of sodium silicate and the like, It is a wet method synthetic silica having an average primary particle size of about several nm to 100 nm. Colloidal silica is available from Nissan Chemical Industries, Ltd. Snowtex ST-20, ST-30, ST-40, ST-C, ST-N, ST-20L, ST-O, ST-OL, ST-S. ST-XS, ST-XL, ST-YL, ST-ZL, ST-OZL, ST-AK and the like are commercially available.

  The colloidal silica used in the glossy expression layer preferably has an average primary particle size in the range of 30 nm to 100 nm from the viewpoint of ink absorbability and gloss. Furthermore, it is preferable to use two or more types of colloidal silica having different average primary particle diameters in combination. In this case, it is more preferable to use a combination of colloidal silica having an average primary particle diameter of 30 nm to less than 60 nm and colloidal silica having an average primary particle diameter of 60 nm to 100 nm, and the average primary particle diameter with respect to the total amount of colloidal silica. The ratio of colloidal silica of 30 nm to less than 60 nm is preferably 60% by mass or more.

The particle shape of the colloidal silica includes a spherical shape, a chain shape (beaded shape), and the like, and a spherical colloidal silica is preferable in terms of the effects of the present invention, particularly scratch resistance and gloss.
The colloidal silica has an anionic property, a nonionic property, and a cationic property, but the stability of the coating solution of the colloidal silica layer, particularly the stability of the coating solution containing polyvinyl alcohol as an organic binder (the colloidal over time of the coating solution). Anionic properties are preferred in terms of silica aggregation and separation.

0.1-8.0 g / m < ² > is preferable and, as for the solid content coating amount of the colloidal silica in a glossiness expression layer, the range of 0.3-5.0 g / m < ² > is more preferable. Thereby, the gloss and scratch resistance can be further improved without lowering the ink absorbability.

  In the ink jet recording medium of the second aspect of the present invention, the glossy layer preferably contains a cationic compound, and a cationic polymer or a water-soluble polyvalent metal compound is preferably used as the cationic compound. The details of these cationic polymers and water-soluble polyvalent metal compounds are the same as those described in the ink receiving layer. In the present invention, the cationic compound used in the colloidal silica layer is preferably a cationic polymer.

  0.1-10 mass% is preferable with respect to colloidal silica, and, as for the addition amount of the said cationic compound, the range of 0.5-8.0 mass% is more preferable.

  The glossy layer preferably further contains an organic binder. The organic binder is preferably used at 10% by mass or less based on colloidal silica, and the lower limit is about 0.5% by mass. More preferably, the organic binder is used in the range of 1 to 7% by mass. By containing the organic binder in this range, the scratch resistance is further improved without lowering the ink absorbability.

  Examples of the organic binder include the organic binders described above used in the ink receiving layer. Among these, a particularly preferable organic binder is completely or partially saponified polyvinyl alcohol or cation-modified polyvinyl alcohol. Particularly preferred among the polyvinyl alcohols are those having a degree of saponification of 80% or more or those completely saponified. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferred.

  The cation-modified polyvinyl alcohol has a primary to tertiary amino group or a quaternary ammonium group in the main chain or side chain of the polyvinyl alcohol as described in, for example, JP-A-61-10383. Polyvinyl alcohol.

  For the glossy layer, a hardener can be used together with an organic binder. Examples of the hardener include the hardeners used in the ink receiving layer described above. Of these hardeners, boric acid or borates are particularly preferably used. Other colloidal silica layers include surfactants, colored dyes, colored pigments, UV absorbers, antioxidants, pigment dispersants, antifoaming agents, leveling agents, preservatives, fluorescent whitening agents, viscosity stabilizers, A pH regulator and the like can be contained.

  The ink jet recording medium according to the second aspect of the present invention comprises a coating liquid for an ink receiving layer mainly comprising at least one inorganic fine particle on a support, and a layer containing a colloidal silica and a cationic compound (gloss development layer). It is important that the pH of the coating liquid for the glossy layer is in the range of 3.3 to 6.0. More preferably, the pH range of the coating liquid for the glossy layer is 3.5 to 5.5.

  By laminating a coating liquid of a colloidal silica layer containing a cationic compound and having a pH in the range of 3.3 to 6.0 on the ink receiving layer, scratch resistance and glossiness are improved. Ink absorbability is greatly improved, and in addition, aggregation at the interface between the ink receiving layer and the colloidal silica layer is eliminated, and coating unevenness and gloss unevenness are eliminated.

  In the ink jet recording medium according to the second aspect of the present invention, the method of applying the glossy layer is a sequential application method (for example, blade coater, air knife coater, roll coater, bar coater, gravure). The effect of the present invention can be obtained by any method of a coater, a reverse coater, etc.) or a multilayer simultaneous multilayer coating method (for example, slide bead coater, slide curtain coater, etc.), but the multilayer simultaneous multilayer coating method is preferable. Used.

Conventionally, the ink receiving layer and the gloss developing layer were generally applied sequentially (method of applying and drying the gloss developing layer after coating and drying the ink receiving layer), but the amount of colloidal silica applied in the gloss developing layer was solid. It was found that the gloss and scratch resistance effects of the glossy layer could not be sufficiently exhibited when sequentially applied when the amount was 8 g / m ² or less and further 5 g / m ² or less. This is because when a relatively thin gloss developing layer is applied on the ink receiving layer mainly containing coated and dried inorganic fine particles, a part of the coating liquid of the gloss developing layer is formed in the voids in the ink receiving layer. This is thought to be due to the penetration of a uniform glossy layer. It is also possible that air present in the voids in the ink receiving layer diffuses into the coating liquid of the upper gloss developing layer to form bubbles, thereby generating crater-like coating defects (crater repellency). It was an obstacle to uniform application.

  Still further, when the vapor phase method silica, alumina, or alumina hydrate having an average primary particle size of 50 nm or less is used as the inorganic fine particles of the ink receiving layer, particularly when the vapor phase method silica is used, these inorganic fine particles are used. In the case where the ink-receiving layer containing is once coated and dried, and then the gloss-developing layer is coated, the ink-receiving layer may be finely cracked in the process of becoming wet again and drying.

  The problem in the case of sequentially applying the relatively thin gloss developing layer as described above after applying and drying the ink receiving layer is solved by simultaneously applying the ink receiving layer and the gloss developing layer. In the present invention, the thin layer application of the gloss developing layer is preferable from the viewpoint of ink absorbability. Colloidal silica is inferior in ink absorbency compared to other inorganic fine particles, for example, vapor phase silica, alumina and alumina hydrate, which are preferably used in the ink receiving layer of the present invention. Is preferably a thin layer. On the other hand, colloidal silica is excellent in gloss and scratch resistance. If a uniform coating surface can be formed, sufficiently high gloss and scratch resistance effects can be obtained even in a thin layer. Therefore, in order to satisfy the high level of ink absorbency, gloss and scratch resistance at the same time, it can be said that it is extremely preferable to apply a thin gloss developing layer simultaneously with an ink receiving layer mainly containing inorganic fine particles.

  In the simultaneous multi-layer coating, a plurality of coating liquids of the ink receiving layer and the gloss developing layer are coated on a support using a coater such as a slide bead coater or a slide curtain coater. In the state where the coating liquid of the ink receiving layer and the gloss developing layer is laminated, a new problem has occurred that aggregation easily occurs at the interface between the two layers. This problem is solved by adding a cationic compound to the glossy layer and adjusting the pH of the coating solution to a range of 3.3 to 6.0, preferably to a range of 3.5 to 5.5. The

Although the preferable structure of a glossiness expression layer is as having mentioned above, about 3-25 mass% is preferable, and, as for the density | concentration of the colloidal silica in the coating liquid of this layer, More preferably, it is 5-15 mass%. About 10-50 g / m < ² > is preferable and, as for the moisture application quantity of a colloidal silica layer coating liquid, 10-30 g / m < ² > is more preferable.

  The support used for the ink jet recording medium of the second aspect of the present invention is the same as the support used for the ink jet recording medium of the first aspect of the present invention, and the preferred aspects are also the same.

  In the ink jet recording medium of the first aspect of the present invention and the ink jet recording medium of the second aspect of the present invention (hereinafter sometimes referred to as “the ink jet recording medium of the present invention”), the support is made of plastic or the like. Any of a transparent support made of a transparent material and an opaque support made of an opaque material such as paper can be used. In particular, in order to take advantage of the transparency of the ink receiving layer, it is preferable to use a transparent support or a highly glossy opaque support. Further, a read-only optical disk such as a CD-ROM or DVD-ROM, a write-once optical disk such as a CD-R or DVD-R, or a rewritable optical disk can be used as a support, and an ink receiving layer can be provided on both sides of the label.

  As described above, the ink jet recording medium of the present invention has an excellent surface shape and excellent ink absorbability. Further, even when an ink containing a highly associative dye is used as in the ink jet recording method described later, the generation of bronzes can be suppressed.

<Inkjet recording method>
An ink jet recording method of the present invention is characterized in that an ink containing a dye represented by the following general formula (I) is ejected onto the ink jet recording medium of the present invention described above to record an image. It is.

In general formula (I), M represents a hydrogen atom or a metal atom or an oxide, hydroxide or halide thereof. Pc represents a (k + l + m + n) -valent phthalocyanine nucleus represented by the following general formula (II). X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—R ₁ , —SO ₂ —R ₁ , —SO ₂ NR ₂ R ₃ , —CONR ₂ R ₃ , —CO ₂ —R ₁ , Or CO-R ₁ and at least one each of the four benzene rings {A, B, C, D in general formula (II)} in the phthalocyanine nucleus. However, X ₁ , X ₂ , X ₃ , and X ₄ are not all the same, and at least one of X ₁ , X ₂ , X ₃ , and X ₄ has an ionic hydrophilic group as a substituent. . R ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₃ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. k represents an integer of 0 <k <8, l represents an integer of 0 <l <8, m represents an integer of 0 ≦ m <8, and n represents an integer of 0 ≦ n <8. However, k, l, m, and n represent numbers satisfying 4 ≦ k + l + m + n ≦ 8. Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ each independently represents a hydrogen atom or a monovalent substituent. Each of the monovalent substituents may further have a substituent.

There is no limitation on the ink jet recording method in the ink jet recording method of the present invention, and a known method, for example, a charge control method in which ink is ejected using electrostatic attraction force, or a drop-on-demand method using vibration pressure of a piezo element ( Pressure pulse method), acoustic ink jet method that converts electrical signal into acoustic beam, irradiates ink and ejects ink using radiation pressure, and thermal that uses ink to form bubbles by heating ink and generate pressure Used for ink-jet systems. Especially, it is preferable to use for a pressure pulse system and a thermal ink inkjet system.
Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

  The dye represented by the general formula (I) will be described. The dye mixture represented by the general formula (I) of the present invention includes a dye mixture and a salt thereof, and a dye mixture and a hydrate thereof. The salt and hydrate may be used alone or in a mixture.

  In the general formula (I), M represents a hydrogen atom, a metal atom, or an oxide, hydroxide or halide thereof. Examples of the metal atom represented by M include Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, etc. are mentioned.

Examples of the metal atom oxide represented by M include VO and GeO.
Examples of the metal atom hydroxide represented by M include Si (OH) ₂ , Cr (OH) ₂ , and Sn (OH) ₂ .
Halides of metal atoms represented by _{M, AlCl, SiCl 2, VCl} , VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like.
Among these, as M, Cu, Ni, Zn, Al, and the like are preferable, and Cu is most preferable.

In the general formula (I), X ₁ , X ₂ , X ₃ , and X ₄ are each independently —SO—R ₁ , —SO ₂ —R ₁ , —SO ₂ NR ₂ R ₃ , —CONR ₂ R _3. , —CO ₂ —R ₁ or CO—R ₁ represents a substituent selected from the four benzene rings in the phthalocyanine nucleus {A, B, C, D in the general formula (II)} Each has at least one. The dye mixture of the present invention is a dye mixture containing dyes having a plurality of different substituents. The central metal of the phthalocyanine nucleus does not differ between dyes.

The substituent is preferably a substituent selected from —SO—R ₁ , —SO ₂ —R ₁ , —SO ₂ NR ₂ R _3, and a set of —SO ₂ —R ₁ and —SO ₂ —R ₂ , or more preferably set between _-SO 2 -R ₁ and _-SO 2 _NR 2 _{R 3,} a set of the _-SO 2 -R ₁ and _-SO 2 -R ₂ are particularly preferred.
However, X ₁ , X ₂ , X ₃ , and X ₄ are not all the same, and at least one of X ₁ , X ₂ , X ₃ , and X ₄ has an ionic hydrophilic group as a substituent. .

In the general formula (I), R ₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted one. A telocyclic group is most preferred.

R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted heterocycle. A ring group is most preferred.

R ₃ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferable.

The substituted or unsubstituted alkyl group represented by R ₁ , R ₂ and R ₃ is preferably an alkyl group having 1 to 12 carbon atoms. In particular, a branched alkyl group is preferred because of increasing the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form). Examples of the substituent further substituting the alkyl group include the same substituents as those in the case where R ₁ , R ₂ , R ₃ and Y described later can further have a substituent. Of these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they enhance the association of the dye and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted cycloalkyl group represented by R ₁ , R ₂ and R ₃ is preferably a cycloalkyl group having 5 to 12 carbon atoms. In particular, the case of having an asymmetric carbon (use in a racemic form) is particularly preferable because of increasing the solubility of the dye and the ink stability. Examples of the substituent further substituting the cycloalkyl group include the same substituents as those in the case where R ₁ , R ₂ , R ₃ and Y described later can further have a substituent. Of these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they enhance the association of the dye and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted aryl group represented by R ₁ , R ₂ and R ₃ is preferably an aryl group having 6 to 12 carbon atoms. Examples of the substituent further substituting the aryl group include the same substituents as those described later when R ₁ , R ₂ , R ₃ and Y can further have a substituent. Among these, an electron-withdrawing group is particularly preferable because the oxidation potential of the dye is noble and fastness is improved. Among them, halogen atom, hetero group, cyano group, carboxyl group, acylamino group, sulfonamido group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, quaternary ammonium group are preferable, cyano group, carboxyl group More preferred are sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, and quaternary ammonium group.

The heterocyclic group represented by R ₁ , R ₂ and R ₃ is preferably a 5-membered or 6-membered ring, which may be further condensed. Further, it may be an aromatic heterocyclic group or a non-aromatic heterocyclic group.

In the following, the heterocyclic group represented by R ₁ , R ₂ and R ₃ is exemplified in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is not limited. Substitution at the 2nd, 3rd and 4th positions is possible. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like.

Among them, an aromatic hetero group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, Thiadiazole is mentioned.
They may have a substituent, and examples of the substituent include the same substituents as those described later when R ₁ , R ₂ , R ₃ and Y can further have a substituent. It is done.

In the general formula (I), k, l, m, and n represent an integer of 0 <k <8, represent an integer of 0 <l <8, represent an integer of 0 ≦ m <8, and 0 ≦ n <An integer of 8 is represented. However, k, l, m, and n represent numbers satisfying 4 ≦ k + l + m + n ≦ 8.
Furthermore, k, l, m, and n represent an integer of 0 <k <8, represent an integer of 0 <l <8, represent an integer of 0 ≦ m <8, 0 = n is preferable, and particularly 0 < represents an integer of k <8, represents an integer of 0 <l <8, preferably m = n = 0, and particularly represents an integer of 0 <k <4, and represents an integer of 0 <l <4 (k + l M = n = 0 is most preferable.

In the general formula (II), Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ and Y ₈ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include halogen atom, alkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryl Oxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy Groups, carbamoyloxy groups, silyloxy groups, aryloxycarbonyl groups, aryloxycarbonylamino groups, imide groups, heterocyclic thio groups, phosphoryl groups, and acyl groups, each of which may further have a substituent. Good.

  Among them, particularly preferred are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and an alkoxycarbonyl group. A halogen atom and a cyano group are preferable, and a hydrogen atom is most preferable. The monovalent substituent preferably has less than 8 carbon atoms.

  The phthalocyanine nucleus represented by the general formula (II) is preferably a phthalocyanine nucleus represented by the following general formula (III).

The ink for inkjet recording used in the present invention can be prepared by dissolving and / or dispersing the dye represented by the general formula (I) in an oleophilic medium or an aqueous medium. Preferably, the ink uses an aqueous medium.
Further, if necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.

  As the drying inhibitor, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration enhancer is preferably used for the purpose of allowing the ink for inkjet to penetrate better into paper. As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants and the like can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, U.S. Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21114, Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8 No. -502911, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, the neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the ink for ink jet recording, the pH adjuster is preferably added to summer for pH 6 to 10 and more preferably pH 7 to 10 for summer. preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink of the present invention is preferably 25 to 70 mN / m. Furthermore, 25-60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the dye represented by the general formula (I) is dispersed in an aqueous medium, it is described in JP-A-11-286637, Japanese Patent Application Nos. 2000-78491, 2000-80259, 2000-62370, etc. As described above, colored fine particles containing a pigment and an oil-soluble polymer can be dispersed in an aqueous medium, or Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, and 2000-203857 can be used. It is preferable to disperse the compound of the present invention dissolved in a high boiling point organic solvent in an aqueous medium as described in each specification. The specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above-mentioned patent publications. be able to. Alternatively, the phthalocyanine compound may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

  It is preferable that 0.1 to 20 parts by mass of the dye represented by the general formula (I) is contained in 100 parts by mass of the inkjet ink used in the present invention. Moreover, you may use together another pigment | dye with the said phthalocyanine compound in the ink for inkjet used for this invention. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  The inkjet ink used in the present invention preferably has a viscosity of 40 cp or less. The surface tension is preferably 20 mN / m or more and 70 mN / m or less. Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.

  The ink-jet ink used in the present invention can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Any yellow dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); for example, coupler components Azomethine dyes having open-chain active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

  Any applicable magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.

  Any applicable cyan dye can be used. For example, aryl or hetaryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Examples include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
Applicable black materials include disazo, trisazo, tetraazo dyes, and carbon black dispersions.

  When an image is formed on the ink jet recording medium of the present invention described above using an ink containing the dye represented by the general formula (I) described above, which is highly associative, it has an excellent surface shape and absorbs ink. In addition to the effect of excellent properties, the effect of suppressing the generation of bronze is also obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the examples, an inkjet recording sheet is prepared as an example of the inkjet recording medium, and “parts” and “%” in the examples represent mass standards unless otherwise specified.
<Example 1>
(Preparation of inkjet recording sheet 1)
The following basic solution A was applied to photographic paper Krispia <High Gloss> manufactured by Seiko Epson Corporation so that the liquid coating amount was 23 g / m ² and dried at 75 ° C. for 5 minutes. The humidity was adjusted for one day in an environment of 60% RH.

[Composition of basic solution A]
(1) Boric acid 2.6 parts (2) Ammonium zirconium carbonate 10.15 parts (Zircosol AC-7 (28% aqueous solution), manufactured by Daiichi Rare Element Chemical Co., Ltd.)
(3) Ammonium carbonate (first grade: manufactured by Kanto Chemical Co., Inc.) 20.0 parts (4) Ion-exchanged water 143.2 parts (5) Polyoxyethylene lauryl ether (surfactant) 24.0 parts (Kao Corporation ), Emulgen 109P (2% aqueous solution))

  A defined by the formula (1) of the obtained inkjet recording sheet 1 was measured by the method described above. The results are shown in Table 1. Moreover, the following evaluation was implemented. The results are shown in Table 1.

(Appearance evaluation)
The surface state of the surface having the ink receiving layer of the obtained inkjet recording sheet 1 was evaluated according to the following criteria.
○: No cracks are observed at all.
Δ: Minute cracks are observed.
X: A big crack is observed.

(Ink absorption time)
The measurement system shown in FIG. 1 was used. A recording head having a piezoelectric element 12, an ink chamber 14, and a nozzle plate 16 is driven by a head driving signal for ejecting ink, and a circuit 22 that generates a time delay of a predetermined time is adjusted. Illumination light is applied to the ink droplet 18 in the vicinity of the flying ink droplet 18 by the lamp 20 for a short period of time, and this is magnified to a predetermined magnification by the CCD camera 24 and imaged. With this configuration, the timing at which the tip of the ink droplet contacts the recording medium and the timing at which all of the ink droplet penetrates into the recording medium are obtained from a plurality of images captured by adjusting the delay time. The permeation time after ink droplet landing was measured.

In this evaluation, the following method was adopted in order to predict the degree of penetration inhibition due to the presence of preceding ink droplets already in the media during the ink penetration into the media. 11 pl of test ink is ejected from an inkjet nozzle at 230 msec intervals (preceding landing). At this time, by moving the medium at a speed of 100 μm / second, ink droplets that land on the medium land at a distance of 23 μm (subsequent landing). The ink absorption time was defined as the time for the ink droplets that subsequently landed to be absorbed by the media.
In the above, ink in an ICC-32 cartridge manufactured by Seiko Epson Corporation was used.

<Example 2>
(Preparation of inkjet recording sheet 2)
For the production of the ink jet recording sheet 1, except for using the photographic paper <gloss> manufactured by Seiko Epson Corporation instead of the photographic paper Chrispier <high gloss> manufactured by Seiko Epson Co., Ltd. An inkjet recording sheet 2 was produced in the same manner as the production of the sheet 1. Evaluation similar to Example 1 was implemented with respect to the obtained sheet | seat 2 for inkjet recording. The results are shown in Table 1.

<Comparative Example 1>
Inkjet recording sheet 3 was prepared in the same manner as in Example 1 except that the basic solution A was not applied. Evaluation similar to Example 1 was implemented with respect to the obtained sheet | seat 3 for inkjet recording. The results are shown in Table 1.

<Comparative example 2>
In Example 2, an inkjet recording sheet 4 was produced in the same manner as in Example 2 except that the basic solution A was not applied. Evaluation similar to Example 1 was implemented with respect to the obtained sheet | seat 4 for inkjet recording. The results are shown in Table 1.

<Comparative Example 3>
(Production of support)
Wood pulp consisting of 100 parts of LBKP is beaten to 300 ml Canadian freeness with a double disc refiner, 0.5 parts of epoxidized behenamide, 1.0 part of anionic polyacrylamide, 0.1 part of polyamide polyamine epichlorohydrin, 0.5 part of cationic polyacrylamide All parts were added at an absolutely dry mass ratio with respect to the pulp, and weighed with a long net paper machine to produce a base paper of 170 g / m ² .

In order to adjust the surface size of the base paper, 0.04% of a fluorescent whitening agent (“Whiteex BB” manufactured by Sumitomo Chemical Co., Ltd.) is added to a 4% aqueous solution of polyvinyl alcohol, and this is 0 in terms of absolute dry mass. The base paper was impregnated to a density of 0.5 g / m ² , dried, and then subjected to a calendering process to obtain a base paper adjusted to a density of 1.05 g / ml.

After the corona discharge treatment was performed on the wire surface (back surface) side of the obtained base paper, high-density polyethylene was coated to a thickness of 19 μm using a melt extruder to form a resin layer composed of a mat surface. (Hereinafter, the resin layer surface is referred to as “back surface”). The resin layer on the back side is further subjected to corona discharge treatment, and thereafter, as an antistatic agent, aluminum oxide (“Alumina sol 100” manufactured by Nissan Chemical Industries, Ltd.) and silicon dioxide (“Nissan Chemical Industry Co., Ltd.” “ Snowtex O ") and a 1: a dispersion dispersed in water at 2 weight ratio, dry mass was coated to a 0.2 g / m ^2.

Furthermore, after the corona discharge treatment is applied to the felt surface (surface) side where the resin layer is not provided, anatase-type titanium dioxide 10%, a trace amount of ultramarine blue, and a fluorescent whitening agent 0.01% (vs. polyethylene) A low-density polyethylene containing MFR (melt flow rate) 3.8 is extruded to a thickness of 40 μm using a melt extruder to form a high gloss thermoplastic layer on the surface side of the base paper. (Hereinafter, this high-gloss surface is referred to as a “front side”), which was used as a support.
A silica fine dispersion was prepared as follows.

(Preparation of silica fine dispersion A-1)
Gas phase method silica 25 parts (average primary particle size 7 nm, specific surface area 300 m ² / g by BET method) (hereinafter referred to as silica) was added to 553 parts of ion-exchanged water stirred at 2000 rpm with a homomixer, Add 0.33 parts of the prescribed amount of dimethyldiallylammonium chloride (Charol DC902P, 50% aqueous solution, Daiichi Kogyo Seiyaku), add 50 parts of silica, and dimethyldiallylammonium chloride (Charol DC902P, 50% aqueous solution, Daiichi Kogyo Seiyaku). 0.67 parts of a prescription amount and 25 parts of silica are added, and then 0.54 parts of zirconyl acetate (Zircosol ZA-30 50% aqueous solution, first rare element industry) is added and dissolved as a water-soluble polyvalent metal compound. 1 at 4000 rpm 30 ° C. with a homomixer (manufactured by Koki Kogyo Kogyo; TK homodisper) 0 min treatment was manufactured a preliminary silica dispersion. This pre-dispersed liquid was further dispersed with a liquid-liquid collision type disperser (Ultimizer, manufactured by Sugino Machine Co., Ltd.) at 130 MPa in one pass to prepare a silica fine dispersion having a silica concentration of about 15% by weight.

(Preparation of ink receiving layer coating liquid A-1)
<Production of co-dissolved product of polyvinyl alcohol, diethylene glycol monobutyl ether (butisenol 20P) and Emulgen 109P (hereinafter referred to as PVA co-dissolved product)>
The following components were mixed under cooling, heated to 90 ° C. and dissolved to obtain a PVA co-dissolved product.
Ion-exchanged water 88.6 parts Emulgen 109P (manufactured by Kao Corporation) 0.23 parts butisenol 20P (manufactured by Kyowa Hakko Chemical Co., Ltd.) 2.1 parts polyvinyl alcohol 7.0 parts ("PVA235" manufactured by Kuraray Co., Ltd.) "Saponification degree 88.5%, polymerization degree 3500)

  Next, to the (1) silica fine dispersion A-1 obtained above, the solution of the (2) PVA co-dissolved product obtained above and the following components (3) to (7) were added. K. Homodisper (made by Koki Kogyo Co., Ltd.) was dispersed again for 20 minutes at a rotational speed of 2000 rpm to prepare a coating liquid A-1 for an ink receiving layer having the following composition.

<Composition of Ink Receiving Layer Coating Liquid A-1>
(1) Silica fine dispersion A-1 58.9 parts (2) PVA co-dissolved product (water-soluble resin) 7.61% aqueous solution 31.2 parts (3) Boric acid (crosslinking agent) 3.9 parts (4 ) Ion-exchanged water 1.3 parts (5) Superflex 650 (Daiichi Kogyo Seiyaku Co., Ltd.) 2.2 parts (6) Ethanol 1.2 parts (7) Polyaluminum chloride (Alphain 83, Daimei Chemical ( Co.) 1.3 parts

Next, each component having the following composition was mixed to prepare a mordant coating liquid B.
<Composition of mordant coating liquid B>
(1) Boric acid (cross-linking agent) 0.65 parts (2) Ammonium carbonate (Kanto Chemical reagent grade 1) 5.0 parts (3) Zirconyl ammonium carbonate (13% aqueous solution) 1.27 parts (Zircozol AC-7 , Made by Daiichi Rare Element Industries)
(4) Ion-exchanged water 87.08 parts (5) Emulgen 109P (10% aqueous solution) (manufactured by Kao Corporation) 6.0 parts

(Preparation of inkjet recording sheet)
The front surface of the support obtained above was subjected to corona discharge treatment, and then the ink receiving layer coating liquid A-1 was applied to the front surface at an application amount of 175 ml / m ² using an extrusion die coater. (Applying step), and dried with a hot air drier at 80 ° C. (wind speed 3 to 8 m / sec) until the solid content concentration of the coating layer reached 20%. The coating layer showed constant rate drying during this period. Before showing the reduction drying, it was immersed in the mordant coating solution B for 3 seconds to adhere 15 g / m ² on the coating layer, and further dried at 80 ° C. for 10 minutes (curing step). Thus, an inkjet recording sheet 5 provided with an ink receiving layer having a dry film thickness of 35 μm was obtained. The pH of the ink receiving layer surface was 4.1. Evaluation similar to Example 1 was implemented with respect to the obtained sheet | seat 5 for inkjet recording. The results are shown in Table 1.

<Example 3>
<Preparation of polyolefin resin-coated paper support 1>
A 1: 1 mixture of hardwood bleached kraft pulp (LBKP) and hardwood bleached sulfite pulp (LBSP) was beaten to 300 ml with Canadian Standard Freeness to prepare a pulp slurry. As a sizing agent, alkylketene dimer is 0.5% to pulp, polyacrylamide is 1.0% to pulp, and cationized starch is 2.0% to pulp. Polyamide epichlorohydrin resin is 0 to pulp. 0.5% added and diluted with water to make a 1% slurry. This slurry was made with a long paper machine so that the basis weight was 200 g / m ² , dried and humidity-controlled to obtain a base paper for a polyolefin resin-coated paper support.

On one side of the above base paper, 10 parts anatase titanium and 0.06 parts fluorescent whitening agent (4,4′-bis) for 100 parts low density polyethylene with a density of 0.918 g / cm ^3. Cooling roll in which (6-methyl-benzoxazol-2-yl) stilbene) is uniformly dispersed, melted at 320 ° C., extrusion coated to 36 g / m ² , and finely roughened. And a polyolefin resin layer on the ink absorbing layer side was provided. On the opposite side of the base paper, 70 parts of high density polyethylene resin density of 0.962 g / cm ³ and a density of 0.918 g / cm ³ low-density polyethylene resin 30 parts blend resin composition was melted at 320 ° C., 31 g A polyolefin resin layer on the backcoat layer side was provided by extrusion coating using a cooling roll that had been extrusion coated so as to be / m ² and roughened.

On one side of the polyolefin resin-coated paper support (the surface on which the ink absorption layer is coated), an undercoat layer having the following composition subjected to high-frequency corona discharge treatment is applied and dried so that the gelatin adhesion amount is 50 mg / m ^2. Then, after the high frequency corona discharge treatment is performed on the opposite surface (backcoat layer coating surface side) of the support, the backcoat layer having the following composition is applied so that the solid content coating amount of the polyurethane resin is 1.0 g / m ^2. And dried. The MD taber stiffness and the whiteness of the polyolefin resin layer on the ink absorbing layer side of the polyolefin resin-coated paper support on which the undercoat layer and the backcoat layer were thus coated were measured. As a result, the Taber stiffness was 3.7 mN · m, and the whiteness was 99%.

<Underlayer>
Lime-processed gelatin 100 parts Sulfosuccinic acid-2-ethylhexyl ester salt 2 parts Chrome alum 10 parts

<Back coat layer>
100 parts of polyurethane resin (Tg 60 ° C.) (Ionomer type polyurethane resin from Dainippon Ink and Chemicals, HW-350)
Surfactant 0.3 part

The polyolefin resin-coated paper support was coated with an ink-receiving layer coating solution (A-2) having the following composition in a solid content coating amount of 25 g / m ² , and a colloidal silica-containing layer (B-1) having the following composition was made of colloidal silica. It apply | coated so that it might become 0.2 g / m < ² > by solid content application amount. Immediately after coating, the film was cooled for 20 seconds in a cooling zone maintained at 0 ° C. and then dried with 60 ° C. air for 3 minutes.
Thereafter, the basic solution A is applied so that the liquid coating amount is 23 g / m ² , dried at 75 ° C. for 5 minutes, then conditioned and dried in an environment of 23 ° C. and 60% RH for one day. A recording sheet 6 was produced. Evaluation similar to Example 1 was implemented with respect to the obtained sheet | seat 6 for inkjet recording. The results are shown in Table 1.

<Coating layer for ink receiving layer (A-2)>
Gas phase method silica 100 parts (average primary particle size 7 nm, average secondary particle size 100 nm)
3 parts of dimethyldiallylammonium chloride homopolymer (Charol DC902P manufactured by Daiichi Kogyo Seiyaku Co., Ltd., molecular weight 9000)
23 parts of polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500)
Thioether compound 3 parts (3,6-dithia-1,8-octanediol)
3 parts of basic polyaluminum hydroxide (Purachem WT manufactured by Riken Green Co., Ltd.)
Boric acid was adjusted with water so that 4 parts solids concentration was 10% by mass.

<Colloidal silica-containing layer (B-1)>
100 parts of PL-3L (Fuso Chemical Co., Ltd. colloidal silica, average primary particle size 32 nm)
It adjusted with water so that solid content concentration might be 0.5 mass%.

<Example 4>
Inkjet recording sheet 7 was prepared in the same manner as in Example 4 except that in Example 3, the colloidal silica coating solution was not applied. Evaluation similar to Example 1 was implemented with respect to the obtained sheet | seat 7 for inkjet recording. The results are shown in Table 1.

<Comparative example 4>
In Example 3, an inkjet recording sheet 8 was produced in the same manner as in Example 3 except that the basic solution was not applied. Evaluation similar to Example 1 was implemented with respect to the obtained sheet | seat 7 for inkjet recording. The results are shown in Table 1.

<Comparative Example 5>
In Example 4, an inkjet recording sheet 9 was produced in the same manner as in Example 4 except that the basic solution was not applied. Evaluation similar to Example 1 was implemented with respect to the obtained sheet | seat 8 for inkjet recording. The results are shown in Table 1.

  From Table 1, it can be seen that the inkjet recording sheets of Examples 1 to 4 have a short ink absorption time and a good surface shape.

<Examples 5-6, Comparative Examples 6-7>
(Preparation of ink 1)
Ultrapure water having a resistance value of 18 MΩ or more was added to the following components to make 100 g, followed by stirring for 1 hour while heating at 30 to 40 ° C. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared the cyan ink liquid (C-1). However, in the following dye 1, two of the four Xs are SO2 (CH2) 3SO3Li, and the two Xs are SO2 (CH2) 3SO2NH (CH3) CH2OH.
C-1:
The following dye 1 4.7g
Urea 2.4g
Triethylene glycol 10.7g
Triethylene glycol monobutyl ether 9.1g
1,2 hexanediol 2.4 g
2-pyrrolidone 3.5g
Glycerin 11.8g
Triethanolamine 0.5g
Proxel XL II 1.0g
Olfin E1010 1.0g

(Inkjet recording)
The ink 1 was loaded into a cyan ink cartridge of an Epson ink jet printer PM-A-700, printed on the ink jet recording sheet shown in Table 2, and evaluated as follows. The results are shown in Table 2.

(Ozone resistance evaluation)
A cyan monochrome stair patch image was printed. After 24 hours from the printing of the staircase patch image, the reflection density of each density region in the staircase patch portion was measured using an X-rite 310 densitometer equipped with a status A filter as a standard (Ci). A fading test was conducted by storing this sample in an ozone gas fading tester at an ozone concentration of 5 ppm for 7 days. The ozonizer was a commercially available apparatus of a high-pressure discharge system with 5 kV AC voltage applied, and the ozone gas concentration was set and controlled using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
After storage for 7 days, the image density was measured again, the density (Cf) after storage was determined, and the dye residual ratio [%] = (Cf / Ci) × 100 was determined and evaluated. As the dye residual ratio, a value at a reflection density Ci of 0.9 to 1.1 was adopted.
Evaluation was made in three stages, with A as the residual ratio of 70% or more, B as 60% or more and less than 70%, and C as less than 60%.

(Bronze gloss occurrence)
The cyan Dmax portion printed in an environment of 30 ° C. and 80% RH was visually observed to confirm the occurrence of bronzing.

  From Table 2, it can be seen that the ink jet recording medium of the present invention has good ozone resistance and no bronzing even when highly associative ink is used.

It is a schematic block diagram of the apparatus for measuring the ink absorption time in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Recording medium 12 Piezo element 14 Ink chamber 16 Nozzle plate 18 Ink drop 20 Lamp 22 Time delay circuit 24 CCD camera

Claims (7)

Having an ink receiving layer on the support;
The peak obtained when the ink-receiving layer is collected and the collected ink-receiving layer is measured by solid ¹¹ B-NMR has an A defined by the following formula (1) of 0.6 or less,
The ink-receiving layer includes a step of applying a coating solution containing at least a boron compound to form a coating layer on a support, and a coating layer formed by applying the coating solution to the coating layer Is formed through a step of applying a basic solution having a pH of 7.1 or higher after declining drying.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm) On the support, it has an ink receiving layer and a glossy expression layer,
The peak obtained when the ink receiving layer and the gloss developing layer are collected and a sample obtained by mixing the collected ink receiving layer and the gloss developing layer is measured by solid ¹¹ B-NMR is defined by the following formula (1). A is 0.6 or less,
The ink-receiving layer includes a step of applying a coating solution containing at least a boron compound to form a coating layer on a support, and a coating layer formed by applying the coating solution to the coating layer Is formed through a step of applying a basic solution having a pH of 7.1 or higher after declining drying.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm)   The inkjet recording medium according to claim 1, wherein the ink receiving layer contains a compound containing a thioether group or a sulfoxide compound.   The ink receiving layer contains a water-soluble resin and inorganic fine particles in a ratio of 0.23 to 0.33 parts by mass of a water-soluble resin with respect to 1 part by mass of the inorganic fine particles. The inkjet recording medium according to any one of 3. A peak obtained when an ink receiving layer is provided on a support, the ink receiving layer is sampled, and the collected ink receiving layer is measured by solid-state ¹¹ B-NMR, is defined as A defined by the following formula (1). A step of applying a coating liquid containing a boron compound on a support at least to form an application layer on an ink receiving layer of an ink jet recording medium having an A of 0.6 or less; and the application to the application layer Inkjet recording characterized by having a step of forming on a support through a step of applying a basic solution having a pH of 7.1 or higher after the coating layer formed by applying the liquid exhibits reduced-rate drying A method for manufacturing a medium.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm) When an ink receiving layer and a gloss developing layer are provided on a support, the ink receiving layer and the gloss developing layer are collected, and a sample obtained by mixing the collected ink receiving layer and the gloss developing layer is subjected to solid ¹¹ B-NMR measurement. The peak obtained by applying an ink-receiving layer of an ink jet recording medium having an A defined by the following formula (1) of 0.6 or less to at least a coating liquid containing a boron compound on a support. After the step of forming a coating layer, and after the coating layer formed by coating the coating solution on the coating layer shows reduced-rate drying, a step of applying a basic solution having a pH of 7.1 or more, A method for producing an ink jet recording medium, comprising a step of forming on a support.
Formula (1)
A = (peak area in the range of 5-10 ppm) / (peak area in the range of -5-5 ppm) An ink jet recording method comprising: recording an image by ejecting ink containing a dye represented by the following general formula (I) onto the ink jet recording medium according to claim 1.

(In the general formula (I), M represents a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. Pc represents a (k + l + m + n) -valent phthalocyanine nucleus represented by the following general formula (II). X ₁ , X ₂ , X ₃ , and X ₄ each independently represent —SO—R ₁ , —SO ₂ —R ₁ , —SO ₂ NR ₂ R ₃ , —CONR ₂ R ₃ , —CO ₂ —. R ₁ or CO—R ₁ is present, and at least one each exists in each of the four benzene rings {A, B, C, D in the general formula (II) in the phthalocyanine nucleus, provided that X is X _{1, X 2,} X 3, _{X 4} are not be all the same, _and, .R ₁ having as X _1, X _2, X 3, at least one substituent an ionic hydrophilic group _{X 4} Is a substituted or unsubstituted alkyl group, substituted or R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₃ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, k represents an integer of 0 <k <8, and l represents 0 <l <8 M represents an integer of 0 ≦ m <8, and n represents an integer of 0 ≦ n <8, where k, l, m, and n represent numbers satisfying 4 ≦ k + 1 + m + n ≦ 8. ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₇ , Y ₈ each independently represents a hydrogen atom or a monovalent substituent, each monovalent substituent further comprising a substituent. (You may have it.)

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