JP2001232934A - Ink jet recording medium, use thereof, and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording medium, with which a high density and high picture quality ink jet recording is possible, and an ink accepting layer especially excellent in transparency and water resistance of an image can be formed. SOLUTION: In the ink jet recording medium, in which at least one layer of ink accepting layers is provided on a support, the ink accepting layer includes fine alumina particles manufactured by a gaseous phase method and a hydrophilic polymer so as to realize the high density, high picture quality, high transparency and high water resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium used in an ink jet recording method using a water-soluble ink, and more particularly, to an image having excellent water resistance, good fixation of ink, high image density and good color development. It relates to a possible ink jet recording medium.

[0002]

2. Description of the Related Art In recent years, an ink jet recording method is a method in which fine droplets of ink are caused to fly according to various operating principles and adhere to a recording medium such as paper to record images, characters, and the like. It has features such as high speed, low noise, easy multi-coloring, great flexibility of recording patterns, and no need for development and fixing. It is rapidly spreading in various applications such as information equipment as a recording device for various images. Furthermore, images formed by the multi-color ink jet method can obtain multicolor printing by the plate-making method or a record comparable to printing by the color photographic method. Since it is cheaper than multicolor printing and printing, it is being widely applied to the field of full-color image recording.

However, the speed of the ink jet recording system has been increased,
With the improvement of performance such as high definition and full color, more advanced characteristics are also required for the image receiving body. Its advanced characteristics are high density of print dots, bright and vivid color tone, quick absorption of ink, ink does not flow or bleed even when print dots overlap, horizontal direction of print dots It is required that the diffusion to the surface is not unnecessarily large and the periphery is smooth and not blurred. In particular, in the case of color printing, not only single-color printing of yellow, magenta, cyan, and black, but also multi-color printing in which these colors are superimposed is performed, and extremely strict performance is required because the ink adhesion amount is further increased.

[0004] Many techniques have been proposed to solve these problems. For example, JP-A-52-907
No. 4 discloses a recording material having a coating layer formed of an inorganic fine powder and a binder, and JP-A-55-51583 discloses a recording paper in which a coating layer containing a non-colloidal silica powder and a polymer binder is provided on a base paper. JP-A-55-144172 discloses a recording method having a pigment coating layer for adsorbing a coloring component in an aqueous ink. JP-A-56-148583 discloses a recording composition mainly composed of finely divided silica and a water-soluble resin. Many techniques using an inorganic powder and a water-soluble binder such as a recording material having a liquid receiving layer provided on a substrate have been proposed. Silica synthesized by the wet method has pores and has been used in many recording media because of its good ink absorbency.However, since silica is anionic, it can fix anionic dyes in the ink. The water resistance was poor, and the light resistance was poor due to the large number of silanol groups on the surface. Further, since the particles are agglomerated, there is no transparency, and it is not suitable for a recording medium having a photographic quality desired in recent years. On the other hand, many techniques using silica synthesized by a gas phase method have been proposed. For example, JP-A-9-32347
Nos. 5, 9-156203, and 10-119423 are techniques for forming a three-dimensional void layer by crushing fine particle silica and mixing it with a hydrophilic polymer.
No. 0-217601 achieves water resistance by adding a cationic mordant.

[0005] Silica synthesized by a gas phase method does not have pores, but mixes with a binder to form a three-dimensional void layer and absorb ink. The fumed silica is an ultrafine particle having a primary particle diameter of about 10 nm, and has a small secondary particle diameter due to a small cohesive force, so that an image receiving layer with good transparency can be obtained. In addition, since silica synthesized by a gas phase method has a very small particle size, gloss can be obtained without performing calendering or the like on the surface,
It is often used for photographic recording paper such as output from a digital video camera.

However, since silica has the same anionicity as the dye in the ink, the fixability of the ink is poor, the image density is low, and the water resistance and the moisture resistance are poor. Therefore, it is necessary to use a binder obtained by modifying a water-soluble polymer serving as a binder with a cation, or to add a cationic polymer or a cationic coupling agent. However, these cationic substances have the property of uniformly promoting the deterioration of the dye in the ink by light, so that a light-fast material had to be further added.

In order to improve water resistance, a technique has been proposed in which cationic inorganic fine particles are contained in an ink receiving layer to improve water resistance. The cationic inorganic fine particles have a good fixation of the ink by the ink jet recording method, and an image having high image density and good color development can be obtained. This is because the dye in the ink used in the ink jet recording method is often an acid dye, and therefore, the effect is obtained by using cationic inorganic fine particles in the ink receiving layer. JP 11
No. 147362 is an ink jet recording medium having, on a support, an ink receiving layer containing ultrafine particles having a positive charge on the surface, such as barium sulfate, zinc oxide, magnesium oxide, lead oxide, and zirconium oxide.
No. 7885 proposes an ink jet recording medium in which a basic porous pigment such as finely divided alumina, synthetic hydrotalcite, phyllosilicate or the like is provided in a ink receiving layer as a dye adsorbent. However, pigments such as alumina synthesized by a liquid phase method have a very large primary particle size, and even fine particles synthesized by a gas phase method such as barium sulfate and zinc oxide can obtain only large particles. Therefore, it is difficult to obtain a transparent medium when used as a recording medium.

[0008] Also, many recording media using alumina hydrate (pseudo-boehmite) as cationic inorganic fine particles have been proposed. As a recording medium of alumina hydrate, for example, JP-A-4-115984 and JP-A-5-3
Japanese Patent Application Laid-Open No. 2414 adjusts the thickness of the particles, Japanese Patent Application Laid-Open No. 8-132731 adjusts the degree of crystallinity, and Japanese Patent Application Laid-Open No. 9-66664 discloses an example in which fine control such as the aging temperature and the period is performed. Japanese Patent Application Laid-Open No. 7-76162 proposes a recording sheet having a silica gel layer on a pseudo-boehmite layer in order to improve the friction resistance of the surface.

[0009]

Among the conventionally developed recording media, silica-based recording media require the addition of a cationic polymer in order to improve water resistance and moisture resistance. Had the disadvantage of causing Also, without adding a cationic polymer, a method of improving the water resistance by containing cationic inorganic fine particles has also been adopted, but synthesized from fine particles or a liquid phase such as alumina produced by a calcining method. Since the inorganic fine particles have a large particle size and a strong cohesive force, they have the drawback that transparency cannot be obtained and the printing density is low. On the other hand, when alumina hydrate (pseudo-boehmite) having good transparency is used for an ink jet recording medium, it has excellent water resistance and ink fixability,
Since a small particle size is desired, a method of synthesizing from aluminum alkoxide is generally employed. However, the method of synthesizing from alkoxide requires expensive raw materials, and the pseudo-boehmite sol requires adjustment of the crystal size and aspect ratio, which takes time to synthesize, resulting in a very high product and economical efficiency. It becomes a problem. Further, since boehmite particles are primary colloid particles, there is a problem that satisfactory ink absorption speed, ink absorption capacity, and water resistance cannot be obtained.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on means for solving these problems, and as a result, have reached the present invention. The present invention relates to a recording medium in which an ink receiving layer is provided on a support,
The present invention relates to a recording medium, characterized in that the ink receiving layer contains alumina fine particles produced by a gas phase method showing high transparency and water resistance and a water-soluble polymer, its use and its production method.

The present invention provides: 1) an ink jet recording medium having at least one ink receiving layer provided on a support, wherein the ink receiving layer comprises:
An inkjet recording medium comprising alumina fine particles and a hydrophilic polymer produced by a gas phase method, 2) the alumina fine particles vaporize aluminum chloride,
The inkjet recording medium according to the above 1), which is alumina fine particles obtained by oxidizing at a high temperature with an oxidizing gas. 3) The inkjet recording medium according to the above 1) or 2), wherein the alumina fine particles are hydrophilic alumina. 4) The inkjet recording medium according to any one of 1) to 3) above, wherein the alumina fine particles are any of amorphous, γ, δ, and θ crystals or a mixture thereof. Has a specific surface area of 50 to 1000 m ²
/ G, the average primary particle diameter of the alumina fine particles is 3 to 100 n / g.
m), 7) an average of 2 particles obtained by aggregating the primary particle diameter of alumina fine particles.
8) The ink jet recording medium according to any one of 1) to 6), wherein the ink receiving layer has a three-dimensional void structure of alumina fine particles and a hydrophilic polymer. The ink jet recording medium according to any one of the above 1) to 7), 9) the ink jet according to any one of the above 1) to 8), wherein the hydrophilic polymer is a nonionic polymer Recording medium; 10) nonionic polymer is polyvinyl alcohol, polyacrylamide, poly N-vinyl formamide, poly N
-Ink jet recording medium according to 9), which is at least one selected from vinylacetamide and modified products and copolymers thereof, 11) mass ratio of alumina fine particles to hydrophilic polymer is 1: 1
20) The inkjet recording medium according to any one of the above 1) to 10), wherein the dye is carried on the ink receiving layer of the inkjet recording medium according to any one of the above 1) to 10). 13) In an inkjet recording method for performing recording by applying droplets of a recording liquid containing a dye to a recording medium, the recording medium is the inkjet recording medium according to any one of 1) to 11). 14) In the production of an inkjet recording medium in which at least one ink receiving layer is provided on a support, alumina fine particles produced by a gas phase method are provided on the ink receiving layer. And a method for manufacturing an ink jet recording medium containing a hydrophilic polymer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The alumina fine particles in the present invention are alumina (aluminum oxide) obtained by vaporizing aluminum chloride or metallic aluminum and oxidizing the same with an oxidizing gas in a gaseous phase. Fixed form, γ
It is a so-called transition alumina of type, δ type, θ type and the like. These particles are of various particle sizes and are not particularly limited, but preferably have an average primary particle size of 3 to 10
0 nm, the primary particles are weakly agglomerated,
m of average secondary particles. The average primary particle size here is the particle size observed with a transmission electron microscope,
The average secondary particle diameter is an average particle diameter obtained by a laser light scattering measurement device.

As the alumina fine particles used in the present invention, those having a specific surface area of 50 to 1000 m ² / g are preferably used. When the specific surface area is less than 50 m ² / g, it is difficult to exhibit sufficient ink absorbency. On the contrary, when the specific surface area exceeds 1000 m ² / g, handling as a powder becomes extremely difficult, and Cause trouble. The primary particle diameter is 3 nm to 50 n.
m is desirable. When the primary particle diameter is less than 3 nm, 1
The space between the secondary particles becomes extremely small, the ability to absorb the solvent and the ink in the ink is reduced, and the desired image quality cannot be obtained. The average primary particle diameter is 50n.
When it exceeds m, the aggregated secondary particles become large, the transparency of the ink receiving layer is reduced, and the voids become small, which is not preferable. Further, when mixing with the water-soluble polymer, it is preferable to disperse in advance in water so that the average secondary particle diameter becomes 50 to 200 nm. Here, the average secondary particle diameter is a value obtained by a laser light scattering measurement device. As a dispersion method, a general disperser for dispersing a pigment can be used, but it is preferable to use a disperser such as a ball mill, a sand mill, a pot mill, a homomixer, a homogenizer, and a nanomizer.

As a method for producing alumina, there is a method in which aluminum hydroxide, aluminum alkoxide, alum and the like are calcined and then pulverized. Aluminum hydroxide, aluminum alkoxide, and alum are calcined to remove water, alcohol, ammonium sulfate, etc., and become alumina.However, calcining increases the primary particle diameter or agglomerates the particles. The particles are not preferable in the present invention because they become particles.

On the other hand, as a method for producing alumina by a gas phase method, for example, a method in which a metal is melted and vaporized in a vacuum vessel and introduced into an oxidizing atmosphere to obtain an ultrafine oxide, And a method of vaporizing and oxidizing a metal halide typified by anhydrous aluminum chloride, etc., and spouting and oxidizing the metal halide into a burner flame are well known. Particles produced by such a gas phase method require transparency because they have a lower degree of agglomeration than alumina produced through the liquid phase, or are very monodisperse in a shape close to a perfect sphere. It is suitable for an ink jet recording medium.

In the ink receiving layer of the present invention, inorganic fine particles other than fine alumina particles are used in combination in order to impart appropriate properties such as color developability and ink absorbency to the extent that the function as the receiving layer is not impaired. No problem. As the inorganic fine particles that can be used in the present invention, silica, titanium dioxide, zinc oxide, zirconium oxide, cerium oxide, barium sulfate, zeolite, calcium carbonate, diatomaceous earth, kaolin, aluminum hydroxide, talc, magnesium oxide,
Examples thereof include inorganic fine particles generally used for paper coating, such as magnesium carbonate.

The hydrophilic resin in the present invention is not particularly limited, but is preferably a nonionic polymer, such as polyvinyl alcohol, polyacrylamide, poly N-vinyl formamide, poly N-vinyl acetamide, Polyvinylpyrrolidone, polyacryloyl morpholine, polyethylene glycol and modified products and copolymers thereof, gelatin or a derivative thereof,
Starch or the like can be used. These may be used alone or in combination of two or more. When the amount of the hydrophilic resin used is small, the strength of the ink receiving layer may be insufficient. On the other hand, when the amount is too large, the amount of ink absorbed or the amount of the dye carried may be low. In 5 to 50% by weight of the total solid content of the coating layer is preferred,
More preferably, it is 10 to 40% by mass.

In the ink receiving layer in the present invention, it is necessary to form a void layer in order to absorb the ink. As a method of forming the void layer, a method of applying a coating solution containing porous inorganic fine particles and a hydrophilic polymer on a support, forming voids between the porous fine particles and the fine particles, adjusting the coating solution of the inorganic fine particles A method of forming voids by forming a three-dimensional structure by agglomeration at the time of or film formation, a method of forming a void by forming a three-dimensional structure by treating the surface of inorganic fine particles with an inorganic or organic substance There are various methods, but any means may be used.

In the present invention, the ink receiving layer contains alumina fine particles, a hydrophilic polymer and the like by dissolving or dispersing the ink receiving layer composition in a diluent comprising water or a water-soluble organic solvent. As the coating liquid, known coating methods such as bar coating, air knife coating, curtain coating, gravure coating, roll coating, spray coating, lip coating, and dip coating, and dipping methods can be used. Drying after coating can be carried out by any of the usual drying methods, for example, hot air heating, electric heater, infrared heater, drum heater and the like.

The solvent for dispersing the components of the ink receiving layer includes water, methanol, ethanol, isopropanol, n-propanol, n-butanol, methyl ethyl ketone, ethyl acetate, acetone, dimethylformamide, dimethylacetamide, methylcellosolve, Ethyl cellosolve, ethylene glycol, propylene glycol and the like can be mentioned. These solvents may be used alone or as a mixture of two or more.

The amount of the inorganic powder is preferably from 50 to 95% by mass on a dry weight basis relative to the total solid content of the coating layer. If the amount is less than 50% by mass, the effect of ink absorption may not be sufficient. If the compounding amount exceeds 95% by mass, the layer strength of the ink receiving layer may decrease. More preferably, 6
0 to 90% by mass.

On the other hand, if the thickness of the ink receiving layer is too small, the dye cannot be sufficiently supported, and only a low color density may be obtained. Conversely, if the thickness is too large, the strength of the ink receiving layer may be reduced, or the transparency may be reduced, and the transparency and texture of the recorded matter may be impaired. The preferred thickness of the ink receiving layer is 1-1.
00 μm, more preferably 20 to 50 μm.

As a material that can be used as the support, a transparent material such as plastic or an opaque material such as paper may be used. In the invention, in order to utilize the transparency of the colorant receiving layer, the support is preferably a transparent support or a high gloss opaque support. Examples of materials that can be used as the transparent support include glass, polyesters such as polyethylene terephthalate, nitrocellulose, cellulose acetate, cellulose esters such as cellulose acetate butyrate, polysulfone, polyphenylene oxide, polyimide, polycarbonate, and polyamide. Can be. Among these, polyesters are preferred, and polyethylene phthalate is particularly preferred. The thickness of the transparent support is not particularly limited, but in the case of a synthetic resin film, a thickness of 50 to 200 μm is preferred because it is easy to handle.

Art paper, as an opaque support having high gloss,
Coated paper, cast coated paper, high gloss paper such as baryta paper used for silver salt photographic supports, polyesters such as polyethylene terephthalate, nitrocellulose, cellulose acetate, cellulose esters such as cellulose acetate butyrate, Polysulfone, polyphenylene oxide, polyimide, polycarbonate, high gloss film made opaque by adding a white pigment etc. to a plastic film such as polyamide, or the above-mentioned various papers, the above-mentioned various plastic films or the surface of a plastic containing a white pigment etc. A film provided with a coating layer of a polyolefin containing or not containing a pigment can be used. Polyolefin-coated paper (paper support having a white pigment-containing polyolefin layer on the surface thereof) generally used as a silver salt photographic support, or special paper having a metal vapor-deposited layer or the like is preferred. Can be used for In particular, a paper support provided with a white pigment-containing polyolefin layer and a polyester film provided with a white pigment-containing polyolefin layer are preferable. The thickness of the opaque support is not particularly limited, but a thickness of 50 to 200 μm is preferred because it is easy to handle. In order to improve the adhesion to the ink receiving layer formed thereon, these supports are subjected to discharge treatment, chemical cleaning treatment, general surface treatment, coupling agents, auxiliaries such as isocyanates, etc. Treatment, installation of an undercoat layer, and the like may be performed.

If necessary, the inkjet recording medium of the present invention may further contain various additives such as a UV absorber, an antioxidant, a dispersant, a fluorescent dye, a pH adjuster, a defoamer, a lubricant, and a preservative. It can be contained. The preferable content of these is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.

The dye used in the recording liquid includes a dye or a pigment. In particular, alkali-soluble compounds are preferable.

Specific examples of dyes include direct dyes such as C.I. I. Direct Black 2, 4,
9, 11, 14, 17, 19, 22, 27, 32, 3
6,38,41,48,49,51,56,62,7
1,74,75,77,78,80,91,105,1
06,107,108,112,113,117,12
2,132,146,151,154,194;
I. Direct Blue 1,2,6,8,10,14,1
5, 22, 25, 34, 69, 70, 71, 72, 7
5,76,78,80,81,82,83,86,9
0, 95, 98, 106, 108, 110, 120, 1
23,158,159,163,165,192,19
3,194,195,196,199,200,20
1,202,203,207,218,236,23
7, 239, 246, 258; C.I. I. Direct Brown 1A, 2, 6, 25, 27, 31, 44, 52, 5
8, 95, 100, 101, 106, 112, 173
194, 195, 209, 210, 211, 222;
C. I. Direct Green 1,6,8,26,2
8, 33, 37, 59, 63, 64; I. Direct orange 6,8,10,26,29,32,39,4
C. 0, 41, 46, 49, 51, 102; I. Direct Red 1,2,4,8,9,11,13,17,2
0,23,24,26,28,31,33,37,3
9,44,46,47,48,51,54,59,6
2,72,75,76,79,80,81,83,9
0,99,101,111,113,145,189,
220, 225, 230, 234; I. Direct violet 1,7,9,12,35,47,48,5
1, 66, 90, 94; C.I. I. Direct Yellow 1,2,4,8,11,12,22,24,26,2
7, 28, 29, 33, 34, 39, 41, 42, 4
4,48,50,51,58,72,85,86,8
7,88,98,100,106,110,132,1
42, 144 and the like.

Examples of the acid dye include C.I. I. Acid Black 1,2,7,16,17,21,24,2
6,28,31,41,48,52,56,58,6
0, 63, 84, 94, 107, 109, 112, 11
8, 119, 121, 122, 123, 131, 15
5,156,172,194,208; C.I. I. Acid blue 1,7,9,15,22,23,25,27,
29, 40, 41, 43, 45, 47, 49, 51, 5
3,55,56,59,62,69,74,77,7
8,83,90,91,92,93,90,92,9
3,102,104,111,113,117,12
0,124,126,145,158,161,16
7,171,175,183,185,193,22
9, 234, 236, 254; C.I. I. Acid Brown 4, 6, 8, 14, 17, 20, 102, 105;
C. I. Acid Green 3,5,9,12,16,1
9, 20, 25, 27, 35, 41, 95; I. Acid orange 1,2,7,8,10,14,19,2
0, 24, 28, 33, 51, 52, 56, 61, 6
3,64,67,74,92,125,127,15
6; I. Acid Red 1,2,4,6,8,1
3,14,15,18,19,21,26,27,3
0, 32, 33, 34, 35, 37, 38, 40, 4
2,45,51,52,54,57,73,80,8
2,83,85,87,88,89,92,94,9
7, 99, 101, 106, 108, 110, 111,
114, 119, 128, 129, 131, 134, 1
35,138,145,151,154,155,16
1,172,176,179,180,183,18
4,186,187,214,243,248,24
9,254,256,257,266,270,28
8,289,296,317,318,337,35
1; I. Acid violet 1,7,9,11,
15, 17, 34, 35, 41, 43, 49, 56, 5
8, 75; I. Acid Yellow 1, 3, 4, 7,
9, 11, 12, 13, 14, 17, 18, 19, 2
3,25,29,34,36,38,40,41,4
2,44,49,53,55,56,59,61,6
2,65,71,72,73,76,78,99,11
1,114,116,118,121,122,12
9,135,161,162,171,172,18
3,199,201 and the like.

Examples of the basic dye include C.I. I. Basic black 2, 8; I. Basic blue 1,3,5,7,9,24,25,26,28,29;
C. I. Basic brown 1,12; C.I. I. Basic green 1, 4; I. Basic Orange 2,
15, 21, 22; I. Basic Red 1, 2,
9, 12, 13, 37; I. Basic violet 1,3,5,7,9,24,25,26,28,2
9; I. Basic Yellow 1, 2, 11, 12,
14, 21, 32, 36 and the like.

Examples of the reactive dye include C.I. I. Reactive Black 1,3,5,6,8,12,1
4; I. Reactive Blue 2,5,7,12,1
3,14,15,17,18,19,20,21,2
5, 27, 28, 37, 38, 40, 41, 71;
I. Reactive Brown 1, 7, 16; C.I. I. Reactive green 5, 7; I. Reactive orange 2, 5, 7, 16, 20, 24; C.I. I. Reactive Red 6,7,11,12,15,17,21,2
3, 24, 35, 36, 42, 63, 66; I. Reactive violet 2, 4, 5, 8, 9; I.
Reactive yellow 1,2,3,13,14,15,
17 and the like.

Examples of food colorings include C.I. I. Food black 2; I. Food blue 3, 4, 5;
C. I. Food green 2, 3; I. Food Red 2,3,7,9,14,52,87,92,94,10
2,104,105,106; C.I. I. Food violet 2; I. Food Yellow 3, 4, 5 and the like.

Examples of the disperse dye include C.I. I. Disperse Blue 1, 3, 14; C.I. I. Disperse Orange 1, 3, 13, 25; C.I. I. Disperse red 1.13, 19; I. Disperse Yellow 3,
5, 7, 9 and the like.

Further, preferred dyes include azo dyes. For example, C.I. I. Acid Black 1, 2
1,24,26,41,48,52,60,63,8
4,94,123; C.I. I. Acid blue 1,7,
9, 15, 25, 27, 43, 45, 47, 59, 6
2,69,77,78,83,90,92,102,1
04, 113, 120, 158, 161, 193;
I. Acid Brown 6,8,14,17,20,1
02, 105; I. Acid Green 3,5
9, 12, 19, 20, 25, 35, 95; I. Acid orange 1,6,7,8,10,14,19,
20, 24, 28, 33, 51, 52, 61, 63, 6
7, 74, 92, 125, 127, 156; I. Acid Red 1,2,13,14,18,27,3
2,33,35,37,42,52,73,85,8
7,88,89,97,99,101,106,11
1,114,128,134,138,145,15
1,154,161,179,180,183,18
6,214,248,249,266,288,29
6,337,351; C.I. I. Acid violet
1, 7, 9, 17, 56, 58; I. Acid Yellow 7, 9, 11, 17, 19, 23, 25, 29,
36, 38, 40, 42, 44, 49, 56, 59, 6
2,65,72,76,99,118,121,12
9,135,161,162,171,183,19
9, 201; I. Direct black 4,17,
19, 22, 32, 38, 80, 91, 122, 15
4; I. Direct Blue 1,2,6,10,1
4,15,22,25,71,76,78,80,9
5,98,159,218; I. Direct brown 2,27,31,52,95,100,222;
C. I. Direct Green 1,6,26,28,3
3,59; C.I. I. Direct orange 6,26,2
9, 32, 39, 40, 46, 102; I. Direct red 2,4,23,24,26,31,37,
39, 54, 62, 75, 76, 79, 80, 81, 8
3,99,111,113,220,234; I.
Direct violet 7, 9, 35, 47, 48,
51, 66; I. Direct Yellow 4,8,1
1,12,22,26,27,29,33,44,5
0,106;

C. I. Dyes not listed in (Color Index) include CAS (Chemical Abstracts Service) numbers 103571-38-6, 103977-11-3, 10
3977-13-5, 104008-60-8, 106414-14-6, 111953-70-9,
111953-71-0, 111953-72-1, 111953-73-2, 112363-27-
6, 121538-22-5, 122302-90-3, 123458-20-8, 123458-2
1-9, 123458-26-4, 123458-27-5, 124953-15-7, 124998
-48-7, 124998-49-8, 124998-51-2, 125604-93-5, 1264
88-46-8, 126488-48-0, 126514-13-4, 126560-69-8, 12
6817-18-3, 135322-33-7, 136821-11-9, 136821-12-0,
136987-84-3, 136987-85-4, 143784-31-0, 145081-06-
7, 145268-49-1, 149598-26-5, 149598-27-6, 149598-3
0-1, 149598-31-2, 149598-34-5, 149632-22-4, 1
4987-86-1, 151407-65-7, 151407-82-8, 168075-44-3,
169762-48-5, 170344-61-3, 173062-58-3, 173062-61-
8, 173062-64-1, 173062-65-2, 173062-66-3, 173398-8
0-6,173584-00-4,173659-42-2,174366-15-5,174366
-16-6, 174366-19-9, 183130-96-3, 186795-55-1, 1908
52-00-7, 190852-01-8, 190852-04-1, 201987-02-2, 20
1987-06-6, 205580-23-0, 205580-24-1, 211935-63-6,
219806-58-3, 27601-28-1, 37790-31-1, 37790-35-5, 3
7790-37-7, 37790-40-2, 37790-41-3, 37790-52-6, 522
38-67-2, 62331-58-2, 62331-60-6, 76544-02-0, 83045
-89-0, 83738-91-4, 90375-37-4, 90375-42-1, 90375-4
7-6, 96384-79-1, 96384-85-9, 96841-16-6, 105985-32
-8, 105985-33-9, 105985-35-1, 105985-48-6, 106206-
11-5, 106610-72-4, 106643-99-6, 121538-27-0, 14102
8-15-1, 141028-16-2, 149598-24-3, 149598-25-4, 149
598-28-7, 149598-29-8, 149598-35-6, 151407-79-3, 1
51407-83-9, 151408-13-8, 159637-52-2, 159637-54-
4, 159637-55-5, 159637-59-9, 163966-02-7, 173062-5
9-4, 173062-60-7, 173062-62-9, 173062-63-0, 179868
-96-3, 179868-98-5, 179869-00-2, 179869-01-3, 1848
89-97-2, 190852-03-0, 193486-82-7, 195325-89-4, 20
0138-09-6, 200138-10-9, 202394-62-5, 202394-63-6,
211935-64-7, 211935-66-9, 211935-68-1, 211935-70-
5,213399-53-2,213399-54-3,213399-55-4,213399-5
6-5, 213399-57-6, 213399-58-7, 213399-59-8, 213399
-60-1,215462-79-6,218281-61-9,220611-17-6,2206
11-19-8, 220611-22-3, 220622-03-7 and the like. These compounds can be used alone or in combination of two or more kinds at an arbitrary ratio.

Examples of the pigment include organic pigments (for example, azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment, phthalocyanine pigment, perylene pigment, perinone pigment, quinacridone pigment, thioindigo pigment, isoindolinone pigment, quinoflurone pigment, Dioxazine pigments,
Anthraquinone pigments, nitro pigments, nitroso pigments, aniline black, etc.), inorganic pigments (for example, titanium white, zinc white, lead white, carbon black, red iron, cadmium red, yellow lead, ultramarine, cobalt blue, cobalt purple, gin Chromate etc.). These compounds can be used alone or in combination of two or more kinds at an arbitrary ratio. The amount of the dye added is about 0.01 to about 15% by mass.
Is preferable. Further, preferably about 0.1 to about 10
% By mass.

The liquid medium of the ink jet recording liquid is preferably an aqueous medium. The aqueous medium is a solvent having a property of being compatible with water, and is not particularly limited. Examples thereof include water; alcohols (e.g., methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, 2,6-hexanetriol, glycerin, etc.); ketones (acetone, etc.); ethers (tetrahydrofuran, 1,4-dioxane, etc.);
Amides (N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylpropionamide, etc.); pyrrolidinones (1-methyl-2-pyrrolidinone, 2-pyrrolidinone, ε-caprolactam, 1 , 3-dimethyl-2-imidazolidinone); glycols (ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, hexylene glycol, diethylene glycol,
Dipropylene glycol, pentanediol, polyethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, etc.). These aqueous media can be used alone or in combination of two or more at an arbitrary ratio. As the usage,
About 50 to about 98% by mass as the total amount of the liquid medium in the recording liquid
Is preferable. In particular, water serves as a main medium in the ink jet recording liquid, and as a water-soluble organic solvent to be mixed, an aqueous medium having a vapor pressure smaller than water that can be stably maintained so that the ratio in the recording liquid does not decrease is selected. Preferably.

As the pigment, a water-soluble dye is preferable, and the amount of the dye is preferably in the range of about 0.01 to about 15% by mass. More preferably, the range is from about 0.1 to about 10% by weight. This inkjet recording liquid has a pH (hydrogen ion concentration index) of about 7 to about 1 due to the stability of the dye and the like.
It is preferably in the range of 3. The method of measuring pH is not particularly limited, but a method of measuring with a commercially available pH measuring device is simple. P using glass electrode pH meter
An H measuring device or the like is often used. The measurement is usually carried out in an aqueous solution at normal pressure (1 atm) and 25 ° C. The method for adjusting the pH is not particularly limited. It can be used by appropriately selecting from known acidic substances and basic substances.

When dispersing the dye, a dispersant (eg, condensed sodium naphthalene sulfonate, an ionic surfactant, a water-soluble resin, a nonionic surfactant, etc.) may be used as necessary. Alternatively, the surface of the pigment particles may be chemically modified by a sol / gel method to increase the affinity for the liquid medium and the dispersibility. If necessary, a preservative or fungicide (eg, sodium dehydroacetate), a chelating reagent (eg, sodium ethylenediaminetetraacetate), a rust preventive (eg, ammonium thioglycolate), an oxygen absorber may be added to the recording liquid. (For example, sodium sulfite etc.),
Antifoaming agent, viscosity modifier, penetrant (for example, lower alcohol,
Carbinols, surfactants, etc.), nozzle drying inhibitors (eg, gluconolactone, sorbitol, etc.) may be added.

[0039]

The present invention will be described below with reference to examples and comparative examples of the present invention, but the present invention is not limited only to these examples.

[0040]

Example 1 Vapor phase alumina UFA160 (manufactured by Showa Titanium Co., Ltd.) obtained by vaporizing aluminum chloride and oxidizing at high temperature with an oxidizing gas (oxygen, water vapor); specific surface area: 160 m ² / g, average primary 80 g
Was poured into 320 g of purified water, and dispersed by a homogenizer at 5000 rpm for 20 minutes to obtain an alumina slurry. 200 g of a 10% aqueous solution of polyvinyl alcohol (PVA217 manufactured by Kuraray Co., Ltd.) was added to the alumina slurry, and the mixture was stirred with a homogenizer at 2,000 rpm for 10 minutes to prepare a coating liquid A. Apply this coating solution A to a thickness of 100 μm.
m white polyester film and transparent polyester film (manufactured by Teijin Limited; U5174, HS74) using a bar coater, and dried with a hot air dryer at 100 ° C. for 5 minutes to form a 30 μm thick dry ink. A receiving layer was formed to obtain a recording medium A of the present invention.

[0041]

Example 2 Instead of vapor phase alumina UFA160,
Gas phase alumina UFA1 obtained by vaporizing aluminum chloride and oxidizing it at high temperature with an oxidizing gas (oxygen, water vapor)
20 (manufactured by Showa Titanium Co., Ltd .; specific surface area: 120 m ²⁾
/ G, average primary particle size of about 10 nm), except that recording medium B was obtained in the same manner as in Example 1.

[0042]

Example 3 Instead of vapor phase alumina UFA160,
Recording medium C in the same manner as in Example 1 except that aluminum oxide C (manufactured by Nippon Aerosil Co., Ltd .; alumina by gas phase method, specific surface area: 100 m ² / g, average primary particle size: about 13 nm) was used.
I got

[0043]

Comparative Example 1 Polyvinyl alcohol (manufactured by Kuraray Co., Ltd .: trade name: PVA21) was added to 386.5 g of alumina sol 520 (manufactured by Nissan Chemical Co., Ltd.) having a solid content concentration of 20.7 mass%.
200 g of the 10% by mass aqueous solution of 7) was added, and the mixture was stirred with a homogenizer at 2,000 rpm for 10 minutes to prepare a coating liquid D. This coating liquid D was coated with a white polyester film or a transparent polyester film (U5174, manufactured by Teijin Limited).
HS74) using a bar coater.
Dry with a hot air dryer at 00 ° C for 5 minutes and dry coat thickness 30
A μm ink receiving layer was formed to obtain a recording medium D of the present invention.

[0044]

Comparative Example 2 80 g of high-purity alumina UA-5105 synthesized from aluminum hydroxide (manufactured by Showa Denko KK; specific surface area: 10 m ² / g, average primary particle size: 250 nm)
Was poured into 320 g of purified water, and dispersed by a homogenizer at 5000 rpm for 20 minutes to obtain an alumina slurry. To this alumina slurry, 200 g of a 10% by mass aqueous solution of polyvinyl alcohol (trade name: PVA217, manufactured by Kuraray Co., Ltd.) was added, and a homogenizer was used to add 2000 g / min.
The mixture was stirred for 10 minutes by rotation to prepare a coating liquid E. This coating liquid E was applied to a white polyester film and a transparent polyester film (manufactured by Teijin Limited; U5174, HS74) using a bar coater, and dried with a hot air dryer at 100 ° C. for 5 minutes to dry coat. A recording medium E of the present invention was obtained by forming an ink receiving layer having a thickness of 30 μm.

[0045]

Comparative Example 3 In Comparative Example 2, a high-purity alumina UA-
5105 is a silica synthesized by a gas phase method (manufactured by Nippon Aerosil Co., Ltd .; trade name AEROSIL300: specific surface area 300 m ² /
g, average primary particle size of about 7 nm)
In the same manner as in the above, recording medium F was obtained. The following evaluations were performed on the recording media A to F, and the results are shown in Table 1.

(A) A commercially available ink jet printer (PM800, manufactured by Seiko Epson Corporation ) is used as a recording medium on an ink-absorbent white polyester film.
C), each of the four color inks of yellow (Y), cyan (C), magenta (M), and black (Bk) is solid printed, and the dried state is touched with a finger, and stains appear or do not appear. Was determined as follows. 〇: Dry in less than 1 minute after printing. Δ: Dry after printing for 1 minute or more and less than 2 minutes. ×: Drying takes 2 minutes or more after printing.

(B) Water resistance : A prescribed amount of water droplets were applied to each image on a dried and dried image as described in (a) above, and ink bleeding was observed.
The three-level evaluation of Δ and × was performed. ：: No bleeding at all △: Slight bleeding ×: Large bleeding

(C) Image Density Image density of a printed and dried image was measured in the same manner as in (a) above, using a Macbeth reflection densitometer.

(D) Haze meter (manufactured by Tokyo Denshoku Technical Center Co., Ltd .; TC-HIIID)
P).

[0050]

[Table 1]

As is apparent from Table 1, the ink jet recording medium containing the alumina (Examples 1 to 3) synthesized by the gas phase method in the ink receiving layer is alumina sol (Comparative Example 1) or fumed silica (Comparative Example). Although the transparency is almost the same as that of 3), it was confirmed that Examples 1 to 3 had higher image density (good ink fixability) and higher water resistance. Also,
The wet-process alumina of Comparative Example 2 has a large average primary particle size as compared with the gas-phase alumina (Examples 1 to 3), and thus has insufficient transparency.

[0052]

The ink jet recording medium containing the alumina fine particles and the hydrophilic polymer produced by the gas phase method of the present invention has an ink fixing property in an ink jet recording ink using an anionic ink because alumina is cationic. Image density), water resistance, and excellent transparency because the primary particle diameter of the alumina fine particles is small and the cohesive force is weak. According to the present invention, it is possible to provide an ink jet recording medium capable of performing high density and high quality ink jet recording and obtaining a recorded matter having excellent water resistance and transparency.

Continued on the front page F term (reference) 2C056 EA13 FC01 2H086 BA01 BA15 BA33 BA35 BA46 BA48 4F006 AA35 AB12 AB20 AB54 BA01 CA01

Claims (14)

[Claims] 1. An ink jet recording medium having at least one ink receiving layer provided on a support, characterized in that the ink receiving layer contains alumina fine particles and a hydrophilic polymer produced by a gas phase method. Ink jet recording medium. 2. The ink jet recording medium according to claim 1, wherein the alumina fine particles are obtained by evaporating aluminum chloride and oxidizing it with an oxidizing gas at a high temperature. 3. The ink jet recording medium according to claim 1, wherein the alumina fine particles are hydrophilic alumina. 4. The method according to claim 1, wherein the alumina fine particles are amorphous, γ-type, δ-type,
4. The ink jet recording medium according to claim 1, wherein the medium is any one of θ-type crystals or a mixture thereof. 5. The specific surface area of the alumina fine particles is from 50 to 10.
The inkjet recording medium according to any one of claims 1 to 4, which has a water content of 00 m ² / g. 6. An alumina fine particle having an average primary particle diameter of 3 to 3.
6. The ink jet recording medium according to claim 1, which has a thickness of 100 nm. 7. The average secondary particle diameter obtained by aggregating the primary particle diameter of alumina fine particles is 50 to 800 nm.
7. The ink jet recording medium according to any one of claims 1 to 6. 8. The ink jet recording medium according to claim 1, wherein the ink receiving layer has a three-dimensional void structure of alumina fine particles and a hydrophilic polymer. 9. The ink jet recording medium according to claim 1, wherein the hydrophilic polymer is a nonionic polymer. 10. The nonionic polymer according to claim 9, wherein the nonionic polymer is at least one selected from polyvinyl alcohol, polyacrylamide, polyN-vinylformamide, polyN-vinylacetamide and modified products and copolymers thereof. The inkjet recording medium according to any one of the preceding claims. 11. The ink jet recording medium according to claim 1, wherein the mass ratio of the alumina fine particles to the hydrophilic polymer is in the range of 1: 1 to 20: 1. 12. A recorded matter in which a dye is carried on the ink receiving layer of the ink jet recording medium according to claim 1. 13. An ink jet recording method for performing recording by applying droplets of a recording liquid containing a dye to a recording medium, wherein the recording medium is the ink jet recording medium according to any one of claims 1 to 11. Characteristic ink jet recording method. 14. In the production of an ink jet recording medium having at least one ink receiving layer provided on a support, said ink receiving layer contains alumina fine particles and a hydrophilic polymer produced by a gas phase method. A method for manufacturing an ink jet recording medium.