JP2002362013A - Ink jet recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink jet recording material, the ink accepting layer of which is excellent in microcrack resistance and has favorable conveyability, ink absorbency and lustrous properties. SOLUTION: In the ink jet recording material, which is formed by providing at least one ink accepting layer on a support, the support is a biaxially oriented film including particles A having the average particle diameter of 0.6 to 8 μm and the ink accepting layer includes fine inorganic particles B, the average particle diameter of primary particles of which is 0.1 μm or less, particles C having the average particle diameter of 1 μm or more and a hydrophilic binder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink-jet recording material having an ink-receiving layer on a plastic film, and more particularly, to scratches and gloss unevenness on the surface of the ink-receiving layer during production, finishing and handling. Hateful,
The present invention relates to an ink-jet recording material having good transportability during printing, high glossiness, and excellent ink texture with high ink absorption.

[0002]

2. Description of the Related Art As a recording material used in an ink-jet recording system, a swellable ink-receiving layer comprising a solvent-swellable binder such as water or an amorphous ink-receiving layer is formed on a support called ordinary paper or ink-jet recording paper. Recording materials provided with a porous ink receiving layer comprising a pigment such as porous silica and a water-soluble binder such as polyvinyl alcohol are known. A porous material is preferable from the viewpoint of ink absorption.

[0003] For example, Japanese Patent Application Laid-Open No. 55-51583,
Nos. 6-157, 57-107879, 57-10
No. 7880, No. 59-230787, No. 62-160
No. 277, No. 62-184879, No. 62-1833
As disclosed in JP-A-82 and JP-A-64-11877, a recording material obtained by applying a silicon-containing pigment such as silica to a paper support together with an aqueous binder has been proposed.

[0004] Also, Japanese Patent Publication No. 3-56552,
No. 188287, No. 10-81064, No. 10
-119423, 10-175365, 1
No. 0-203006, No. 10-217601, No. 11-20300, No. 11-20306, No. 1
JP-A-134481 and the like disclose a recording material using fine particles of silica synthesized by a gas phase method (hereinafter referred to as gas phase silica). The fumed silica is an ultrafine particle having an average primary particle diameter of several nm to several tens of nm, and is characterized by high gloss and high ink absorption. However, since they are ultrafine particles, there is a problem that scratches and uneven gloss are easily generated on the surface of the ink receiving layer.

Further, JP-A-62-174183, JP-A-2-276670, JP-A-5-32037, JP-A-6-199034 and the like disclose recording materials using alumina or alumina hydrate. ing. Generally, as compared with fumed silica, the glossiness of white paper was good, but the ink absorbency was insufficient, the scratch resistance was easily reduced, and uneven gloss was likely to occur.

[0006] On the other hand, paper has conventionally been generally used as a support for the ink jet recording material, and the paper itself has a role as an ink absorbing layer. In recent years, while a photo-like recording sheet has been demanded, a recording sheet using a paper support has problems such as gloss, texture, water resistance, cockling (wrinkles or wavy) after printing, and is water-resistant. For example, a resin support paper (polyolefin resin-coated paper) in which a polyolefin resin such as polyethylene is laminated on both sides of a paper support, a plastic film, and the like have been used. However, unlike the paper support, these water-resistant supports have a high smoothness on the surface provided with the ink receiving layer, and are likely to cause scratches and uneven gloss on the ink receiving surface during production, finishing, and handling. Was. Further, since the support itself has no ink absorbing property, the ink receiving layer is thick, and the smoothness and gloss are high, so that scratches are more likely to occur and uneven gloss is more conspicuous. In particular, a plastic film is mainly produced by a biaxial stretching method, and when used as a support, an ink jet recording material having excellent texture can be obtained.
No. 9-11606, No. 9-234948, No. 11-268404, No. 2000-37835, No. 2
No. 001 to 10,000. However, in particular, when a plastic film containing particles having a large average particle diameter is used as a support, and when the ink receiving layer is porous using inorganic fine particles, paper or a polyolefin resin-coated paper is used as the support. It was found that minute scratches and uneven gloss were not easily observed in the ink receiving layer.

[0007] Further, there is an increasing demand for further increasing the printing speed in ink jet, and in order to obtain higher ink absorbency, measures have been taken to reduce the content ratio of the binder to the inorganic fine particles in the ink receiving layer. By reducing this ratio, the ink receiving layer was more easily damaged.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing an ink jet recording material provided with an ink receiving layer containing inorganic fine particles, using a biaxially stretched plastic film containing particles having a large particle size as a support. Prevents scratches and uneven gloss on the surface of the ink receiving layer during printing, finishing, and handling, and hardly causes minute scratches and uneven gloss during transport and handling (hereinafter referred to as "small scratches"). Another object of the present invention is to provide an ink jet recording material having high glossiness, high ink absorbency, and high texture with good transportability in a printer.

[0009]

An object of the present invention is to provide an ink jet recording material having at least one ink receiving layer on a support, wherein the support has an average particle size of 0.6.
A biaxially stretched plastic film containing at least one kind of particles A having an average particle size of 0.1 μm or less,
This was achieved by an ink jet recording material containing particles C having a particle size of μm or more and a hydrophilic binder.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The biaxially stretched plastic film used as a support in the present invention will be described.

The polymer used for the biaxially stretched plastic film is not particularly limited, and thermoplastic polymers such as polyesters, polyolefins, polyamides, polystyrenes, polyethers, polyvinyls, polyurethanes, polyacetals, polysulfonates, etc. Polymers. In particular, polyesters are preferable from the viewpoint of cost and thermal stability, and examples thereof include polyethylene terephthalate having an aromatic dicarboxylic acid as a main acid component and an aliphatic glycol as a main glycol component.

The biaxially stretched plastic film of the present invention contains particles A having an average particle size of 0.6 to 8 μm, so that a film having good flatness and gloss and excellent slipperiness can be obtained with high production efficiency. In addition, when used as a support for a recording material, transportability in a printer is improved. For example, barium sulfate, titanium oxide, silica, alumina, alumina hydrate,
Inorganic pigments such as silicon oxide, kaolin, talc, calcium carbonate, zinc oxide, and magnesium oxide, and organic pigments such as benzoguanamine particles, polystyrene particles, and polyacrylic particles are used. The preferred range of the average particle size of the particles A is 0.6 to 3 μm. Particles A generally comprise from 0.01 to 1% by weight of the plastic film, preferably from 0.05 to 1%.
-0.8% by weight. If the amount is too large, the flatness and glossiness are lowered and the film becomes non-uniform.

In the biaxially stretched plastic film of the present invention, besides the particles A, as a white pigment for improving opacity and whiteness, particles D having an average particle size of 0.1 or more and less than 0.6 μm are used.
Is preferable, since the printed image of the recording material obtained by ink jetting becomes sharp. As the particles D, at least one of titanium oxide, barium sulfate, calcium carbonate, silica and the like is used. The particles D are contained in an amount of 3 to 25% by weight, preferably 5 to 20% by weight based on the total solid content of the plastic film. The average particle size of the particles A and B is the average particle size of the primary particles or the secondary particles, and can be obtained by averaging the numerical values obtained by observing the surface and the cross section of the plastic film with an electron microscope.

The biaxially stretched plastic film of the present invention may contain, in addition to the particles A and D, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, aluminum stearate and magnesium stearate. Fatty acid metal salts, antioxidants such as Irganox 1010, Irganox 1076, and blue pigments and dyes such as cobalt blue, ultramarine, cecilian blue, and phthalocyanine blue;
Magenta pigments and dyes such as cobalt violet, fast violet, and manganese violet, and various additives such as a fluorescent whitening agent and an ultraviolet absorber are appropriately used in combination.

The biaxially stretched plastic film is produced according to a conventionally known production method. A polymer containing a predetermined amount of the particles A and D is melt-formed to form an amorphous film. An unstretched film is obtained, stretched in a biaxial direction, heat-fixed, and, if necessary, relaxed. The biaxially stretched plastic film may be composed of two or more layers,
For example, the layer containing the particles A and the layer not containing the particles A are simultaneously formed by melt extrusion and then biaxially stretched in the same manner as described above, but the ink receiving layer is formed on the layer not containing the particles A. It is preferable to provide them from the viewpoint of transportability, smoothness and glossiness of the ink receiving layer. The thickness of the biaxially stretched plastic film used in the present invention is 50 μm or more. If the thickness is less than 50 μm, the texture will be inferior, and there is no particular upper limit, but it is preferably 300 μm or less. If the thickness is more than 300 μm, handling of the recording material becomes inconvenient, and the cost per unit area increases.

An undercoat layer may be provided on the surface of the biaxially stretched plastic film used in the present invention on which the ink receiving layer is to be applied. The undercoat layer is a layer which has been applied and dried on a support before the ink receiving layer is applied. The undercoat layer mainly contains a water-soluble polymer or polymer latex capable of forming a film. Preferred are water-soluble polymers such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble cellulose, and particularly preferred is gelatin. The adhesion amount of these water-soluble polymers is preferably 10 to 500 mg / m ² , and 20 to 300 m / m ^2.
g / m ² is more preferred. Further, the undercoat layer preferably further contains a surfactant and a hardener. Before applying the undercoat layer, corona discharge is preferably performed.

On the surface of the biaxially stretched plastic film of the present invention opposite to the surface on which the ink receiving layer is provided, a film can be formed to the extent that the transportability during printing does not decrease for the purpose of improving the scratch resistance of the surface of the ink receiving layer. A backing layer mainly composed of a water-soluble polymer, polymer latex or the like may be provided. The coating amount of the backcoat layer depends on the shape of the backcoat layer-coated surface of the biaxially stretched plastic film, but is generally 20 to 2000 mg / m ² in solid content, and 100 to 100 mg / m ^2.
0 mg / m ² is preferred.

In the present invention, the inorganic fine particles B having an average primary particle size of 0.1 μm or less used in the ink receiving layer.
As light calcium carbonate, heavy calcium carbonate,
Magnesium carbonate, kaolin, titanium dioxide, zinc oxide, zinc hydroxide, calcium silicate, magnesium silicate,
Examples include silica, synthetic silica, alumina, alumina hydrate, aluminum hydroxide, magnesium hydroxide and the like.

Synthetic silica, alumina and alumina hydrate are selected from the viewpoint of high print density, clear image and low production cost, and among them, fumed silica and alumina hydrate are preferable.

The inorganic fine particles B contained in the ink receiving layer of the present invention comprise 50% by weight based on the total solid content of the ink receiving layer.
Or more, preferably 60% by weight or more, more preferably 70% by weight.
% By weight or more. If the content is more than 92% by weight, the strength of the ink receiving layer is reduced, cracks are liable to occur, the problem of powder scattering in the manufacturing process and the processing process occurs, and scratches are liable to occur when handling printed products. If the amount is less than 50% by weight, the ink absorbency decreases.

The synthetic silica used in the present invention includes those obtained by a wet method and those obtained by a gas phase method. Usually, silica fine particles often refer to wet process silica. As wet silica, silica sol obtained by metathesis of sodium silicate with an acid or the like through an ion exchange resin layer, or colloidal silica obtained by heating and aging this silica sol, gelling silica sol, and changing the production conditions Silica such as those obtained by heating and producing silica gel in which primary particles of several μm to 10 μm are three-dimensional secondary particles having siloxane bonds, and further, silica sol, sodium silicate, sodium aluminate, etc. There are synthetic silicate compounds and the like as main components.

The fumed silica is also called a dry method with respect to a wet method, and is generally produced by a flame hydrolysis method. Specifically, a method of making silicon tetrachloride by burning it with hydrogen and oxygen is generally known, but instead of silicon tetrachloride, silanes such as methyltrichlorosilane and trichlorosilane may be used alone or in a silicon tetrachloride. And can be used in a mixed state. The fumed silica is Aerosil from Nippon Aerosil Co., Ltd. and QS from Tokuyama Co., Ltd.
It is commercially available as a type and can be obtained.

The average particle size of the primary particles of the fumed silica of the present invention is preferably from 5 to 50 nm. In order to obtain higher gloss, the average particle size is from 5 to 20 nm and the specific surface area by the BET method is from 100 to 400 m ² / m. g is preferably used. The BET method referred to in the present invention is one of the methods for measuring the surface area of a powder by a gas phase adsorption method, and is a method for determining the total surface area of 1 g of a sample, that is, the specific surface area, from an adsorption isotherm. Usually, nitrogen gas is often used as the adsorbed gas, and a method of measuring the amount of adsorption from the change in pressure or volume of the gas to be adsorbed is most often used. The most prominent one for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, Teller equation, which is called the BET equation and is widely used for determining the surface area. The surface area is obtained by calculating the amount of adsorption based on the BET formula and multiplying the area occupied by one adsorbed molecule on the surface.

When a fumed silica is used, a recording material having good ink absorption and high gloss can be obtained, but the cohesion of secondary particles is weak because of a small amount of silanol groups on the silica surface.
It has the disadvantage of being easily scratched. Due to this disadvantage, scratches during production, finishing and handling are problematic,
This can be solved by the present invention.

The alumina or alumina hydrate preferably contained in the ink receiving layer of the present invention is aluminum oxide or a hydrate thereof, which may be crystalline or amorphous, amorphous, spherical, plate-like or the like. What has a form is used. Either of them may be used or both may be used, but those having an average primary particle size of 5 to 50 nm are preferably used. Particularly, a plate-like alumina hydrate having an aspect ratio of 2 or more is preferable.

As the alumina of the present invention, γ-alumina which is a γ-type crystal of aluminum oxide is preferable.
Group crystals are preferred. γ-alumina has one primary particle
Although it can be reduced to about 0 nm, secondary particle crystals of several thousands to tens of thousands of nm are usually reduced to 50 to 3 nm by an ultrasonic wave, a high-pressure homogenizer, a facing collision type jet pulverizer, or the like.
Those pulverized to about 00 nm can be preferably used.

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

The alumina or alumina hydrate dispersion aid of the present invention uses an acidic compound, such as lactic acid, acetic acid, formic acid,
Acids such as nitric acid, hydrochloric acid, hydrobromic acid and aluminum chloride are used, but inorganic acids are preferred because of their higher viscosity at low temperatures. The general addition amount of the present invention is 0.1 to 5% by weight based on alumina or alumina hydrate. The use of boric acid or borate as a cross-linking agent for a binder by using alumina dispersed with an acid or alumina hydrate results in good coating solution properties and good coating properties. It is preferable because the glossiness and the ink absorption are improved.

The ink receiving layer of the present invention may be composed of two or more layers for different purposes. The uppermost layer is for improving glossiness and scratch resistance, and the lower layer is for improving ink absorption. In particular, the uppermost layer farthest from the support contains alumina or alumina hydrate having an average primary particle size of 5 to 50 nm, and the other layer contains fumed silica having an average primary particle size of 5 to 50 nm. An ink jet recording material having excellent gloss and ink absorbency can be obtained. The amount of alumina or alumina hydrate is used in the uppermost layer of the ink receiving layer is preferably from 1 to 15 g / m ^2, the range of 1 to 10 g / m ² is more preferable. When the content is more than the above range, the ink absorbency tends to decrease, and when the content is less, the gloss tends to decrease.

In the present invention, the amount of the inorganic fine particles B in the ink receiving layer is preferably from 10 to 35 g / m ² , and from 13 to 30 g / m ^2.
The range of g / m ² is more preferable. If the amount of the inorganic fine particles B is larger than the above range, cracks are likely to occur, and if the amount is small, the ink absorbency is reduced.

The average particle size of the primary particles of the inorganic fine particles of the present invention is defined as particles dispersed to such an extent that the primary particles can be discriminated or 100 particles existing within a certain area by observing the surface or cross section of the plastic film with an electron microscope. The average particle size was determined by defining the diameter of a circle equal to the projected area of each particle as the particle size of the particle. Similarly, secondary particles were obtained by observing particles dispersed with a gentle shearing force using an electron microscope.

Various inorganic particles and organic particles can be used as the particles C having an average particle size of 1 μm or more used in the ink receiving layer of the present invention. Examples of the inorganic particles include silica, synthetic silica, alumina, and alumina hydrate. Products, aluminum hydroxide, calcium carbonate, magnesium carbonate, titanium dioxide, clay, kaolin, talc and the like. Examples of the organic particles include polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyacrylamide, polyvinyl chloride, and the like, and copolymers thereof, a urea resin, a melamine resin, and the like.
It is more preferable that the average particle diameter of the particles C be equal to or larger than the average particle diameter of the particles A contained in the plastic film from the viewpoint of scratch resistance. Although there is no particular upper limit on the average particle size of the particles C, it is generally 30 μm or less, preferably 20 μm or less in consideration of the touch and gloss. As the particles C, two or more kinds of particles having different average particle diameters may be used in combination, and the combination of the particles described below is particularly preferable.

The particles C of the ink receiving layer of the present invention preferably contain at least one kind of particles having an average particle diameter of 1 μm or more and less than 8 μm and at least one kind of particles having an average particle diameter of 8 μm or more. However, inorganic particles are more preferable from the feeling of touch. The particle C is preferably larger than the thickness of the ink receiving layer. In particular, when two or more ink receiving layers are laminated, the case where the above two types of spherical particles are contained in the uppermost layer is preferable from the viewpoint of scratch resistance and glossiness.
The average particle size of the particles C having a size of not less than μm is preferably larger than the thickness of the uppermost layer. Although there is no particular upper limit on the average particle size of the particles C, it is preferable from the tactile sensation that the particles do not protrude more than 10 μm from the ink receiving layer. The average particle size of the particles C is
It is the average particle size of primary particles or secondary particles.

The reason why the combined use of particles having an average particle diameter of 1 μm or more, less than 8 μm, and 8 μm or more as the particles C of the present invention has better scratch resistance than the case where each is used alone is presumed as follows. Is done. That is, even if the particles having a particle diameter of 8 μm or more are used alone, the projections are generated on the surface of the ink receiving layer, so that the scratch resistance and the blocking property are improved. It is presumed that the scratch resistance is greatly improved because it acts as a buffering agent for the surface. In particular, the present invention is highly effective in preventing the occurrence of micro scratches.

1 μm contained in the ink receiving layer in the present invention
The solid content of the particles C is generally 0.005 to 0.8 g / m ² , and preferably 0.01 to 0.5 g / m ² . Particularly when used for the uppermost layer, the solid content is 0.005 to 0.3.
When the amount is within the range of g / m ² , it is possible to obtain a resin having particularly good resistance to micro scratches and excellent ink absorption and gloss. When particles having an average particle diameter of 1 μm or more and less than 8 μm and 8 μm or more are used in combination as the particles C, the content ratio of the latter to the former is preferably 10 to 120% by weight.

In the present invention, the transportability at the time of printing of an ink jet recording material is improved by incorporating particles having a specific average particle size into a plastic film. There is a proposal to improve the paper-passing property by incorporating particles of 5 to 15 μm in the backing layer of the recording material of the resin-coated paper support to improve the paper-passing property. Even when inorganic fine particles are used, no fine scratches as in the present invention are generated due to the rubbing of the front and back surfaces. In the case of a biaxially stretched plastic film containing large particles, the reason that the protruding particles cause micro scratches and uneven gloss on the ink receiving layer is not clear, but even the particles protruding on the plastic film surface that can not be understood by touch. In addition to being firmly fixed to the film, the elasticity of the film itself is large compared to paper or resin-coated paper, so there is little buffering action,
When the film surface comes into contact with the ink receiving layer and rubs, the same portion on the front and back is repeatedly rubbed by repeated application of minute vibrations, especially when transporting a plurality of stacked sheets,
It is presumed that fine scratches and uneven gloss occur.

By using particles C having an average particle diameter of 1 μm or more, preferably 1 μm or more and less than 8 μm and 8 μm or more in the ink receiving layer of the present invention, inorganic fine particles B are contained in a biaxially stretched plastic film containing particles A. The reason why a good ink-jet recording material can be obtained, which has good micro scratch resistance and no gloss unevenness even when the ink receiving layer is provided,
Generally, since the thickness of the ink receiving layer is smaller than the thickness of the plastic film, the particles C are more likely to protrude from the surface of the ink receiving layer than the particles A on the back surface of the film.
Is larger than the average particle size of the particles A,
Is larger than the protruding height of the particles A protruding from the back surface of the plastic film, and the protruding particles C prevent the ink receiving layer from being damaged. In particular, the particles C include particles having an average particle diameter of 8 μm or more. In such a case, it is assumed that the micro scratch resistance is greatly improved.

The ink receiving layer of the present invention has a binder in order to maintain the properties as a film, but a hydrophilic binder which has high transparency and can obtain higher ink permeability is preferably used. In using the hydrophilic binder, it is important that the hydrophilic binder does not swell during the initial permeation of the ink and does not block the voids,
From this viewpoint, a hydrophilic binder having a relatively low swelling property at around room temperature is preferably used. Particularly preferred hydrophilic binders are fully or partially saponified polyvinyl alcohols or cationically modified polyvinyl alcohols. For dispersion of fumed silica, a commonly known disperser such as a high-pressure homogenizer and a ball mill can be used.

Particularly preferred among polyvinyl alcohols are those partially or completely saponified with a saponification degree of 80% or more. Polyvinyl alcohol having an average degree of polymerization of 500 to 5000 is preferred.

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

Although a binder other than the hydrophilic binder can be used in combination, it is preferable that the amount is 20% by weight or less based on the hydrophilic binder. The amount of the hydrophilic binder is preferably 35% by weight or less of the ink receiving layer from the viewpoint of ink absorbability. The content is particularly preferably 8 to 25% by weight, but the ink receiving layer is easily damaged by rubbing or the like, so that the measures according to the present invention are necessary.

In the present invention, the ink receiving layer preferably contains an amphoteric surfactant. As the amphoteric surfactant,
Examples include carboxyammonium betaine type, sulfoammonium betaine type, amino acid type, ammonium sulfate betaine type, imidazolinium betaine type, and the like, US Pat. No. 3,843,368, JP-A-59-4.
No. 9535, No. 63-236546, No. 5-30
No. 3205, No. 8-262742, No. 10-28
No. 2619, and the like.

By adding an amphoteric surfactant to the ink receiving layer, it is possible to prevent scratches and uneven gloss on the surface of the ink receiving layer during winding storage and handling, although the reason is not clear. . It is expected that the structure of the inorganic fine particles in the ink receiving layer becomes moderately flexible due to the amphoteric surfactant, and that scratches are less likely to occur because the external force due to rubbing or the like is reduced.

The amount of the amphoteric surfactant is generally 0.05 to 10% by weight of the ink receiving layer, preferably 0.1 to 5%.
% By weight. If it is less than 0.05% by weight, the effect of preventing abrasion or the like during winding and storage is small, and if it is more than 10% by weight, the strength of the ink receiving layer is reduced and cracks are liable to occur.

In the present invention, preferably, the ink receiving layer contains a water-soluble metal compound to prevent cracking. Therefore, it is possible to reduce the amount of the hydrophilic binder and increase the amount of the attached inorganic fine particles in order to improve the ink absorption.

As the water-soluble metal compound, for example, a water-soluble polyvalent metal salt is selected from calcium, barium, manganese, copper, cobalt, nickel, aluminum, iron, zinc, zirconium, chromium, magnesium, tungsten, and molybdenum. Water-soluble salts of the metals. 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, cupric chloride, copper ammonium chloride (II)
Dihydrate, copper sulfate, cobalt chloride, cobalt thiocyanate, cobalt sulfate, nickel sulfate hexahydrate, nickel chloride hexahydrate, nickel acetate tetrahydrate, nickel ammonium sulfate hexahydrate, nickel amide sulfate Tetrahydrate, aluminum sulfate, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, aluminum chloride hexahydrate, ferrous bromide, ferrous chloride, ferric chloride, sulfuric acid Ferrous, ferric sulfate, zinc bromide,
Zinc chloride, zinc nitrate hexahydrate, zinc sulfate, zinc phenolsulfonate, zirconium acetate, zirconium chloride,
Zirconium chloride octahydrate, zirconium hydroxychloride, chromium acetate, chromium sulfate, magnesium sulfate,
Magnesium chloride hexahydrate, magnesium citrate nonahydrate, sodium phosphotungstate, sodium tungsten citrate, 12 tungstophosphoric acid n hydrate, 12 tungstosilicic acid 26 hydrate, molybdenum chloride, 12 molybdophosphoric acid n-hydrate and the like.

In the present invention, it is preferable to include a cationic polymer in order to improve water resistance. Examples of the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, and JP-A-59-20696.
Nos. 59-33176, 59-33177, 59-15088, 60-11389, and 60
No. 49990, No. 60-83882, No. 60-10
No. 9894, No. 62-198493, No. 63-494
No. 78, No. 63-115780, No. 63-28068
No. 1, JP-A-1-40371, JP-A-6-234268
Polymers having a primary to tertiary amino group and a quaternary ammonium base described in JP-A Nos. 7-125411 and 10-193776 are preferably used. The molecular weight of these cationic polymers is preferably 5,000 or more, more preferably about 5,000 to 100,000.

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

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

In the present invention, the ink receiving layer preferably contains a hardener together with a hydrophilic binder. Specific examples of the hardener include formaldehyde, aldehyde compounds such as glutaraldehyde, diacetyl,
Ketone compounds such as chloropentanedione, bis (2-
(Chloroethyl urea) -2-hydroxy-4,6-dichloro-1,3,5 triazine, U.S. Pat. No. 3,288,7
No. 75, a compound having a reactive halogen, divinyl sulfone, a compound having a reactive olefin as described in U.S. Pat. No. 3,635,718, and an N-type compound as described in U.S. Pat. No. 2,732,316. Methylol compounds, isocyanates described in U.S. Pat. No. 3,103,437, U.S. Pat. Nos. 3,017,280 and 2,
No. 983,611, aziridine compounds, carbodiimide compounds described in US Pat. No. 3,100,704, epoxy compounds described in US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid And dioxane derivatives such as dihydroxydioxane; inorganic hardeners such as chromium alum, zirconium sulfate, boric acid and borate;
They can be used alone or in combination of two or more. Among these, boric acid or borate is particularly preferred. The addition amount of the hardener is preferably from 0.1 to 40% by weight based on the hydrophilic binder constituting the ink receiving layer,
More preferably, it is 0.5 to 30% by weight.

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

In the present invention, the method of applying the ink receiving layer, the undercoat layer, and the backing layer is not particularly limited, and a known coating method can be used. For example, there are a slide bead method, a curtain method, an extrusion method, an air knife method, a roll coating method, a ked bar coating method, a bar coater method, a dip method, and the like.

[0053]

EXAMPLES The present invention will be described below in detail with reference to examples, but the contents of the present invention are not limited to the examples.
Parts and% represent parts by weight and% by weight, respectively.

Example 1 <Preparation of Biaxially Stretched Polyester Film Support> Using dimethyl terephthalate and ethylene glycol as raw materials, a transesterification catalyst for manganese acetate, a polymerization catalyst for antimony trioxide, and polyethylene terephthalate using phosphorous acid as a stabilizer Was manufactured. Particles A shown in Table 1 are dispersed and added in ethylene glycol, and a predetermined amount is contained in a polymer. Based on polyethylene terephthalate obtained, 8% by weight of particles D as anatase type titanium oxide (average particle diameter 0.2 μm) Is dried and melt-extruded to obtain a stretching temperature of 9
The film was biaxially stretched at 0 to 120 ° C, a longitudinal magnification of 3.2 times, and a lateral magnification of 3.5 times, and heat-set at 220 ° C to obtain a 180 µm-thick biaxially stretched polyester film.

After subjecting one surface of the biaxially stretched polyester film to a high-frequency corona discharge treatment, a subbing layer having the following composition was coated and dried so that the gelatin content was 50 mg / m ² , to prepare a support. In addition, a part represents a weight part.

<Undercoat layer> Lime-treated gelatin 100 parts Sulfosuccinic acid-2-ethylhexyl ester salt 2 parts Chromium alum 10 parts

A coating liquid of an ink receiving layer having the following composition, using fumed silica as particles B and two kinds of spherical particles as particles C, was applied to the undercoat layer surface of the above support with a slide coating apparatus and dried. The ink receiving layer coating solution shown below was prepared so that the fumed silica had a solid content of 9% by weight. This coating solution is coated with fumed silica at a solid content of 20%.
g / m ² and dried.

[0058] <Ink receiving layer coating solution> 100 parts of fumed silica (average primary particle size 7 nm, specific surface area 300 meters ² / g by BET method) dimethyl diallyl ammonium chloride homopolymer 4 parts (manufactured by Dai-ichi Kogyo Seiyaku Co., , Sharol DC902P, molecular weight 9000) Spherical particles 0.5 part (Asahi Glass Co., Ltd. silica particles H121, average primary particle diameter 12 μm) Spherical particles 1 part (Sekisui Chemical Co., Ltd. polystyrene, SBX-6, average primary particle diameter 6 μm) Boric acid 3 Part Polyvinyl alcohol 20 parts (Saponification degree 88%, average polymerization degree 3500) Amphoteric surfactant 0.5 part (betaine type; manufactured by Nippon Surfactant, Swanol AM)

The ink-jet recording material prepared as described above was evaluated for scratch resistance, ink absorption and glossiness of the ink receiving layer by the following methods. Table 2 shows the results.

<Scratch Resistance of Ink Receiving Layer> The ink jet recording material was cut into sheets of A4 size, two front and back sides were overlapped, and a 50 g weight was placed thereon. Was rotated three times around the center, microscopic scratches on the ink receiving layer were visually observed, and evaluated according to the following criteria. ；: Micro scratches and uneven gloss were not observed on the ink receiving layer. Δ: Fine scratches and uneven gloss were observed on the ink receiving layer, but there was no problem in practical use. X: The ink receiving layer was markedly scratched and gloss unevenness was remarkably unpractical.

<Ink Absorbency> The recording material for ink jet was printed with a solid black with an ink jet printer MJ-5100C manufactured by Seiko Epson Corporation at 23 ° C. and 55% RH, and after 30 seconds, PPC paper was overlaid on the print surface and lightly pressed. After peeling off, the show-through of the ink on the PPC paper was evaluated. ；: No show-through. △: There is some show-through. ×: There is clearly show-through.

<Conveying property>
100 sheets were continuously printed with an inkjet printer MJ-5100C manufactured by Seiko Epson Corporation at 3 ° C. and 55% RH, and the transportability was evaluated. ；: Double feed did not occur at all. Δ: Double feed occurred once or twice. X: Double feed occurred three or more times.

<Glossiness of Ink Receiving Layer> An unprinted ink jet recording material was visually evaluated according to the following criteria. ；: Very good, close to photographic paper. Δ: Good at the level of art and coated paper. X: Very bad, close to mat paper.

Example 2 An ink jet recording material of Example 2 was obtained in the same manner as in Example 1 except that the type and content of the particles A were changed as shown in Table 1. Table 2 shows the results of the evaluation performed in the same manner as in Example 1.

Examples 3 to 5 Examples 3 to 5 were carried out in the same manner as in Example 1 except that the type and amount of the particles C of the ink receiving layer coating liquid were changed as shown in Table 1. To obtain an inkjet recording material,
Table 2 shows the results of the evaluation performed in the same manner as in Example 1.

Example 6 An ink receiving layer was provided on an undercoating layer in the same manner as in Example 1 except that the biaxially stretched polyester film was replaced with a support using a two-layer film produced as follows. An ink jet recording material of Example 6 was obtained. Table 2 shows the results of the evaluation performed in the same manner as in Example 1.

Using dimethyl terephthalate and ethylene glycol as raw materials, polyethylene terephthalate was produced using manganese acetate as a transesterification catalyst, antimony trioxide as a polymerization catalyst, and phosphorous acid as a stabilizer. Particles A shown in Table 1 are dispersed and added in ethylene glycol, and a predetermined amount is contained in a polymer. Based on polyethylene terephthalate obtained, 6% by weight of anatase-type titanium oxide (average particle diameter of 0.2 μm ) And the polyethylene terephthalate composition obtained without containing the particles A are each dried and melt-extruded simultaneously in two layers to obtain a stretching temperature of 90%.
The film was biaxially stretched at ~ 120 ° C, a longitudinal magnification of 3.2 times, and a lateral magnification of 3.5 times, and heat-set at 220 ° C to obtain a biaxially oriented polyester film having a thickness of 180 µm. The layer containing the particles A was 20 μm.

After the high-frequency corona discharge treatment was applied to the surface of the biaxially stretched polyester film not containing the particles A, the undercoat layer having the same composition as in Example 1 was coated with 50 m of gelatin.
g / m ² was applied and dried to prepare a support.
In addition, a part represents a weight part.

Example 7 In Example 1, the ink receiving layer was a lower layer close to a support having the following composition, and an upper layer having the following composition using two types of spherical particles as particles C. 14g solids
/ M ² , and a recording material for inkjet of Example 7 was obtained in the same manner as in Example 1 except that the upper layer of alumina hydrate was applied so as to have a solid content of 6 g / m ² . Table 2 shows the results of the evaluation performed in the same manner as in Example 1.

<Coating Solution for Ink Receiving Layer Lower Layer> 100 parts of fumed silica (average primary particle size: 12 nm, specific surface area by BET method: 200 m ² / g) Dimethyl diallyl ammonium chloride homopolymer: 4 parts (Daiichi Kogyo Seiyaku Co., Ltd.) Manufactured and manufactured by Sharoll DC902P, molecular weight 9000) Boric acid 3 parts Polyvinyl alcohol 15 parts (Saponification degree 88%, average polymerization degree 3500) Amphoteric surfactant 0.3 parts (betaine, Swam)

<Coating Solution for Upper Layer of Ink Receiving Layer> Alumina Hydrate 100 parts (pseudo boehmite, average primary particle size 15 nm, flat plate with aspect ratio 5) Dimethyl diallyl ammonium chloride homopolymer 4 parts (Daiichi Kogyo Seiyaku Co., Ltd.) Spherol DC902P, molecular weight 9000) Spherical particles 1 part (Asahi Glass Co., Ltd. silica particles H121, average primary particle diameter 12 μm) Spherical particles 1 part (Sekisui Chemical Co., Ltd. polystyrene, SBX-6, average primary particle diameter 6 μm) Boric acid 3 parts Polyvinyl alcohol 15 parts (Saponification degree 88%, average polymerization degree 3500) Amphoteric surfactant 0.3 parts (betaine type; manufactured by Nippon Surfactant, Swanol AM)

Example 8 Ink jet of Example 8 was carried out in the same manner as in Example 1 except that the ink receiving layer had the following composition and the coating amount of alumina hydrate was 25 g / m ² in terms of solid content. Recording material was obtained. Table 2 shows the evaluation results.

<Ink receiving layer coating liquid> Alumina hydrate 100 parts (pseudo-boehmite, average primary particle diameter 15 nm, flat plate with aspect ratio 5) Dimethyl diallyl ammonium chloride homopolymer 4 parts (Daiichi Kogyo Seiyaku Co., Ltd.) , Sharol DC902P, molecular weight 9000) Spherical particles 1 part (Asahi Glass Co., Ltd. silica particles H121, average primary particle diameter 12 μm) Spherical particles 1 part (Sekisui Chemical Co., Ltd. polystyrene, SBX-6, average primary particle diameter 6 μm) Boric acid 3 parts Polyvinyl Alcohol 15 parts (Saponification degree 88%, average polymerization degree 3500) Amphoteric surfactant 0.3 part (betaine type; manufactured by Nippon Surfactant, Swanol AM)

Comparative Example 1 An ink-jet recording material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the particles C of the ink-receiving layer coating liquid were removed, and evaluated in the same manner as in Example 1. did. Table 2 shows the results.

Comparative Example 2 A biaxially stretched polyester film prepared in the same manner as in Example 1 except that the particles A were omitted, and the same procedure as in Example 1 was carried out except that the ink receiving layer coating solution from which the particles C were removed was used. In the same manner, a recording material for inkjet of Comparative Example 2 was obtained. Table 2 shows the evaluation results.

Comparative Example 3 Example 5 was repeated except that the biaxially stretched polyester film produced in the same manner as in Example 5 except that the particles A were omitted.
In the same manner as in the above, an inkjet recording material of Comparative Example 3 was obtained. Table 2 shows the evaluation results.

[0077]

[Table 1] (Note) Particle size is average particle size in μm. The amount of the particles A is% by weight based on the total solid content of the polyester film. The amount of the particles C is based on 100 parts of the inorganic fine particles B in the layer to be added.

[0078]

[Table 2] ────────────────────────────── Glossy ink absorption Scratch resistance Transportability ─────── ─────────────────────── Example 1 ○ ○ ○ ○ Example 2 ○ ○ ○ ~ △ ○ Example 3 ○ ○ ○ ○ Example 4 ○ ○ ○ to △ △ Example 5 ○ ○ △ △ Example 6 ○ ○ ○ ○ Example 7 ○ ○ ○ ○ Example 8 ○ ○ ○ ○ Comparative Example 1 ○ ○ × △ Comparative Example 2 ○ ○ △ × Comparative Example 3 ○ ○ △ × ──────────────────────────────

Results: The ink-jet recording materials of Examples 1 to 8 of the present invention were excellent in transportability, ink absorbency, and gloss, and showed that the ink receiving layer was not easily damaged by microscopic scratches during handling. Example 5 is a case where the average particle size of the particles C is smaller than that of the particles A, but the micro scratch resistance and the transportability were at the practical lower limit. Example 6 is a case in which the support is formed into a two-layer structure in Example 1, and the ink receiving layer is provided on the layer not containing the particles A. The surface properties such as were further excellent. Example 7 was a case where alumina hydrate was used as the particles B of the upper layer of the ink receiving layer. The gloss was superior to that of Example 1, and other characteristics were also superior to those of Example 1. Example 8 is a case in which alumina hydrate was used in place of fumed silica in the ink receiving layer in Example 1, except that the gloss was better than in Example 1 and the ink absorption was slightly reduced. Good characteristics were shown. In Comparative Example 1 in which the particles C of the ink receiving layer were removed in Example 1, the micro scratch resistance was poor, large scratches occurred, and the sample could not be used. In Comparative Example 2 in which the particles A of the support film and the particles C of the ink receiving layer were removed in Example 1, the transportability was poor, and the scratch resistance of the ink receiving layer did not cause micro scratches as in Comparative Example 1. Some large scratches occurred. In Comparative Example 3 in which the particles A of the support film were removed in Example 5, the transportability was poor, and no fine scratches occurred, but some large scratches occurred. In addition, the recording materials for ink jet of Examples 1 to 8 did not cause large scratches.

[0080]

According to the present invention, there has been obtained an ink jet recording material which is excellent in the micro scratch resistance of the ink receiving layer, and has excellent transportability, ink absorption and gloss.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2C056 FC06 2H086 BA15 BA16 BA19 BA33 BA35 BA45

Claims (8)

[Claims] 1. An ink-jet recording material comprising at least one ink receiving layer provided on a support, wherein the support contains at least one kind of particles (A) having an average particle size of 0.6 to 8 μm. An axially stretched plastic film,
Inorganic fine particles (B) having an average primary particle size of 0.1 μm or less, particles (C) having an average particle size of 1 μm or more,
And a hydrophilic binder. 2. The method according to claim 1, wherein the support has an average particle size of 0.1 μm or more.
2. The ink jet recording material according to claim 1, comprising at least one kind of particles (D) having a particle size of less than 0.6 [mu] m. 3. The ink jet recording material according to claim 1, wherein the average particle diameter of the particles C is equal to or larger than the average particle diameter of the particles A. 4. The ink-jet recording material according to claim 1, wherein said biaxially stretched plastic film is a biaxially stretched polyester film. 5. The ink-jet recording material according to claim 1, wherein the inorganic fine particles B are fumed silica having an average primary particle diameter of 5 to 50 nm. 6. The ink-jet recording material according to claim 1, wherein the inorganic fine particles B are alumina or alumina hydrate. 7. The ink receiving layer according to claim 1, wherein the ink receiving layer comprises two or more layers, and the inorganic fine particles B in the layer farthest from the support are alumina or alumina hydrate having an average primary particle diameter of 5 to 50 nm. 7. The ink-jet recording material according to any one of 6. 8. The method according to claim 1, wherein at least one kind of particles having an average particle diameter of 1 μm or more and less than 8 μm and at least one kind of particles of 8 μm or more are used in combination as the particles C.
8. The recording material for inkjet according to any one of items 7 to 7.