JP3088147B2 - Recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material suitable for ink-jet recording with a water-based ink, and in particular, has excellent ink receptivity during recording and excellent recording quality, and is liable to occur when paper is used as a substrate. The present invention relates to a recording material that prevents paper from being loosened due to ink absorption.

[0002]

2. Description of the Related Art Ink jet recording systems are used in various fields as various printers because they have low noise, can perform high-speed recording, and can easily be multicolored. Efforts have been made to improve recording devices and ink compositions so that so-called plain paper such as high-quality paper and coated paper can be used as a recording material used in the ink jet recording method.

However, at present, the recording material has not been satisfactory, and the recording material has been improved in accordance with the improvement of the performance of the recording apparatus such as higher speed and higher definition of recording and the expansion of applications such as full color recording. On the other hand, more advanced characteristics are required. That is, the recording material absorbs the ink quickly and does not bleed or stain. The diffusion of the ink dots in the horizontal direction is not unnecessarily large and uniform. It is required that the density be high and clear; that the recorded image be not discolored or faded by the influence of light during storage or oxygen in the air.

Several proposals have been made to meet these requirements. For example, a coating layer (ink receiving layer) mainly composed of a pigment and a binder having good ink absorbency on a base material
A method of providing a recording medium has been attempted from the early stage of the development of ink jet recording paper (Japanese Patent Application Laid-Open Nos. 58-110287 and 59-18).
No. 5690), by using a xerogel-based porous pigment in which a large number of fine primary particles are gathered and granulated as a secondary aggregate, the ink is formed by using the porous pigment particle gaps and the internal pores of the porous pigment. For example, there is a method of obtaining an ink jet recording sheet having a large ink absorbing capacity and a high ink absorbing speed.

[0005] However, the ink jet recording papers obtained in these proposals are excellent in the intended ink receptivity and can achieve a high color density recording, but have a sufficient improvement in the sharpness of the recording colors. No effect was obtained. Further, in these proposals, it is necessary to control the coating amount in order to obtain a record having excellent ink receptivity and good image quality, that is, for example, until a peak is observed in a pore distribution curve by a mercury intrusion method. In addition, it was necessary to provide a relatively thick coat layer. As a result, the ink jet recording paper had relatively low surface strength, and had drawbacks in writability, printability, and the like, and was liable to generate paper dust during handling.

Therefore, these proposals cannot sufficiently cope with the improvement of the performance of the apparatus and the expansion of applications, and further improvement in the ink receptivity, recording quality and preservation of the recorded image is required. That is the current situation.

On the other hand, with respect to ink, not only a dye is simply dissolved in distilled water, but also a surfactant, a small amount of an organic solvent,
Various attempts have been made to increase the permeability, such as adding an alkaline substance such as monoethanolamine. However, because of this, the water in the ink does not stay only in the ink receiving layer, but easily penetrates into the base material, especially when plain paper is used as the base material, because the base material is unevenly stretched by the water. However, if the recording paper is bumpy or severe during printing, the recording paper may come into contact with the ink nozzle head, causing clogging of the ink nozzle head,
The recording paper may become dirty or torn. Such a phenomenon is more likely to occur as the amount of ink ejected per unit area of the recording paper increases.

In recent years, attention has been paid to color recording by an ink jet recording method. In order to increase the number of colors that can be expressed by an ink jet printer, it is necessary to mix colors of ink. Means that the amount of inevitably increases. Therefore, it has become an issue to improve the phenomenon (so-called bumpiness) that the recording paper is blurred during printing as described above.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material for ink jet recording which is excellent in ink receptivity during recording and recording quality. Still another object of the present invention is to provide a recording material in which the paper is prevented from being loosened due to ink absorption.

[0010]

In view of this situation, the present inventors have conducted intensive studies on the improvement of a recording material for ink-jet recording, and have found that an intermediate layer containing a xerogel-based porous pigment and a xerogel-based porous pigment have been developed. The present invention was completed by combining an ink receiving layer as a main component.

According to the present invention, there is provided a recording material in which an ink receiving layer containing a xerogel-based porous pigment as a main component is provided on a substrate, wherein the ink receiving layer is a BE.
A layer containing at least two xerogel-based porous pigments having different pore radii (peak values) measured by the T method, and a xerogel-based porous pigment is provided between the substrate and the ink receiving layer. A recording material comprising at least one intermediate layer including:

According to the present invention, there is provided a recording material having an ink receiving layer comprising a xerogel-based porous pigment as a main component on a base material, wherein the base material and the ink receiving layer are separated from each other. A recording material characterized by comprising an intermediate layer containing at least two xerogel-based porous pigments having different pore radii (peak values) measured by a BET method.

[0013]

The xerogel-based porous pigment referred to in the present invention includes, for example, (a) a hydrogel-forming substance such as aluminum hydroxide, alumina, silica, and magnesium oxide as a raw material, and drying such hydrogel to form a xerogel. After, grinding,
(A) granulating in a hydrogel state to an appropriate size of secondary and tertiary aggregates, drying and subjecting the mixture to a method described in JP-A-56-120608;
As disclosed in Japanese Patent Application Laid-Open No. H10-197, etc., a method of promoting sintering, crystallization, etc. by further heating to strengthen the bond between the primary particles of the oxide; (c) colloidal silica, colloidal alumina, etc. Urea-formalin resin, melamine-formalin resin and the like are produced in the fine particle suspension water of the above, and the production conditions are adjusted as disclosed in US Pat. No. 3,855,172.
After making the fine particles granulated to the intended secondary particle size,
A method in which the particles are dried and used, or if necessary, further fired to be used as sintered particles; and the like, and can be produced using various known methods.
Many are also commercially available.

Above all, silica pigments provide a recording material having excellent ink receptivity and excellent recording density because of its relatively small refractive index and easy control of the porous structure. Various products such as SYLOID (manufactured by Fuji Devison Co., Ltd.), Mizukasil (manufactured by Mizusawa Chemical Industry Co., Ltd.), and Fine Seal (manufactured by Tokuyama Soda Co., Ltd.) are commercially available and relatively inexpensive. Therefore, it is advantageous and advantageous in terms of economy.

As such xerogel porous pigments, those which are porous and in the form of fine particles are preferable because they exhibit sufficient ink receptivity. Above all, average particles having a specific surface area (nitrogen method) of not less than 200 m ² / g by the BET method and 0.5 to 15 μm (coulter counter: AP = 50 μm measured value) in the form of dispersed particles in the coating liquid. Those having a diameter are preferably used. In particular, the specific surface area is 250 m ² /
g or more and a porous pigment having an average particle diameter of 2 to 10 μm is desirable because it effectively contributes to efficient transfer of the aqueous ink medium to the base material and retention of the coloring component. By the way, if the specific surface area is small, the ink receptivity will be insufficient,
Staining may occur, and if the average particle diameter is 0.5 μm or less, the sharpness of the recorded image is lost, and the recorded image tends to be dull. In addition, the average particle diameter is 15 μm
Exceeding the range may result in uneven spread of the ink dots in the horizontal direction, or loss of sharpness of the recorded image.

According to the first aspect of the present invention, the ink receiving layer contains B
At least two kinds of xerogel-based porous pigments having different pore radii (peak values) measured by the ET method are contained, and at least an intermediate layer containing the xerogel-based porous pigment is provided between the substrate and the ink receiving layer. The feature is that one layer is provided. The present inventors have found that by including at least two types of xerogel-based porous pigments having different pore radii (peak values) measured by the BET method in the ink receiving layer, it is possible to control ink receptivity. Although the application has already been filed (Japanese Patent Application No. 2-121467), by providing at least one intermediate layer containing a xerogel-based porous pigment between the base material and the ink receiving layer, the ink receiving property and the recording image quality are improved. It is excellent, and the unevenness of the paper due to ink absorption is efficiently improved.

According to a second aspect of the present invention, in a recording material having an ink receiving layer containing a xerogel-based porous pigment as a main component, a pore radius measured by a BET method between the ink receiving layer and the substrate is used. (Peak value) is characterized by providing a layer containing at least two types of xerogel-based porous pigments having different peak values,
By providing this layer, it is possible to control the ink receptivity without increasing the thickness of the coat layer, and to provide uniform ink absorption, so that the unevenness of the recording material is also improved.

For example, a porous pigment having a small average particle diameter, in which the pore radius (peak value) is larger than the pore radius (peak value) of a porous pigment having a large average particle diameter, is selected. By using this, the ink receptivity can be improved without causing print thinning even when recording with relatively small ink droplets. Further, by selectively using a pore radius (peak value) of the porous pigment having a large average particle diameter is larger than the pore radius (peak value) of the porous pigment having a small average particle diameter used in combination, Even when printing with relatively large ink droplets, it is possible to improve sharpness and improve ink acceptability without causing print thickening. Furthermore, since these effects are achieved without unnecessarily thickening the coat layer, the obtained recording material is excellent in writability, printability, etc., and can be handled according to plain paper. Become. A layer containing at least two kinds of pigments having such properties as main components can make the movement of the aqueous medium in the ink droplets toward the support uniform.

When at least two or more xerogel-based porous pigments are selectively used, it is important to control the pore distribution (nitrogen method) measured by the BET method. That is, 30
Having a peak of pore radius at ~ 150 ° and 20 to 20
A xerogel-based porous pigment having a total pore volume at 0 ° of 0.5 ml / g or more is selected. Where the pore radius is 20 °
If it is less than 200 °, the ink receptivity is inferior, and if it exceeds 200 °, the sharpness decreases. Also, preferably the pore radius (peak value)
Are selected and used so as to differ from each other by 10 ° or more, particularly advantageous embodiments can be obtained since the effects of the present invention are remarkable.

The xerogel-based porous pigment used in the present invention is usually dispersed and mixed in a hydrophilic medium by various dispersers and used as an aqueous coating. In this case, if a water-soluble protective colloid agent is used, the coating stability is reduced. It is preferable because it is excellent in water retention and the like.

Examples of the water-soluble protective colloid agent include proteins such as gelatin, albumin, casein and soy protein, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose and methylcellulose, agar, sodium alginate, gum arabic, carboxy-modified starch, and cations. Natural and semi-synthetic polymer compounds such as saccharoses such as modified starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly (meth) acrylic acid and copolymers thereof, maleic anhydride copolymer salts and, if necessary, anions Addition-polymerizable synthetic high molecular compounds such as oligomers or polymers having a water-soluble group and / or a cationic group, polyethyleneimine resin, polyamine resin, polyamide resin It can be suitably selected from polyamide epichlorohydrin resin, polyamine epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resin, such as such as dicyandiamide resins condensed synthetic polymer compound such as a water-soluble protective colloid agent.

Most of the xerogel-based porous pigments are heated to impart appropriateness to the technical field, particularly to strengthen the bonding force between primary particles and to develop a porous crystal structure. It is often used after processing. These so-called dry-granulated porous pigments are difficult to prepare paint because the hydrophilicity of the surface is reduced to the inside of the micropores due to the desorption of water adsorbed on the surface, etc. And there are problems with paint properties such as paint fluidity, dispersion stability and water retention. Also, because of poor wetting of the pigment surface with the aqueous medium, it is necessary to use a large amount of binder in order to obtain sufficient adhesive strength, and therefore, dry-granulated porosity selected to have excellent ink receiving ability Although the properties of pigments have not been sufficiently exhibited, they can be improved by using a water-soluble protective colloid agent. Above all, a nitrogen-containing water-soluble resin has a remarkable effect of improving the wettability, and therefore has particularly low foaming and good fluidity. Further, it is preferably used because a paint having good stability can be obtained.

The water-soluble protective colloid is appropriately selected, and if necessary, used in combination of two or more, and the amount of use is not particularly limited.
It is appropriately selected in consideration of workability and the like, but is generally at least 0.1% by weight, preferably 1 to
It is used in a range of about 50%.

As long as the function and effect of the present invention are not impaired, for example, various suitability such as imparting writability, imparting proper equipment, controlling ink absorptivity, controlling paint aptitude, controlling paint physical properties, controlling drying properties, and controlling appearance of recording paper. For application, other pigments, binders, various auxiliaries, and the like are further added, if necessary, to form a coating liquid for the ink receiving layer or a coating liquid for the intermediate layer. A recording material is obtained.

Other pigments include, for example, calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, Inorganic pigments such as amorphous silica, aluminum hydroxide, alumina, and lithopone; organic or organic / inorganic composite pigments such as styrene plastic pigments, acrylic plastic pigments, microcapsule pigments, urea resin pigments, and melamine resin pigments For example, pigments known in the general pigment coating field are exemplified.

Examples of the binders include natural or semi-synthetic polymers such as oxidized starch, etherified starch, carboxymethylcellulose, hydroxyethylcellulose, casein, gelatin, soybean protein, polyvinyl alcohol and derivatives thereof, and polyethyleneimine resins. , Polyvinylpyrrolidone resin, poly (meth)
Acrylic acid or its copolymer, maleic anhydride copolymer, acrylamide resin, (meth) acrylate resin, polyamide resin, polyurethane resin,
(Unsaturated) Synthetic water-soluble resins such as polyester resin, polyvinyl butyral resin, alkyd resin, epoxy resin, epichlorohydrin resin, urea resin, melamine resin, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer Conjugated diene-based polymer latexes such as coalesces, acrylic acid esters, acrylic polymer latexes such as methacrylic acid ester polymers or copolymers, vinyl-based polymer latexes such as ethylene-vinyl acetate copolymer, Alternatively, resins known in the art, such as functional group-containing modified polymer latexes in which an anionic group and / or a cationic group are added to these various polymers, are exemplified, and used alone or in combination. Can be The amount of these binders to be used can be arbitrarily selected in consideration of the required recording suitability of the recording medium, suitability for use, smear suitability of the coating liquid for the ink receiving layer or the coating liquid for the intermediate layer, etc. Has a pigment content of 1-2
00% by weight, preferably in the range of 5 to 50% by weight.

If necessary, pigment dispersants, thickeners, flow improvers, defoamers, foam inhibitors, foaming agents, release agents, penetrants, wetting agents, heat gelling agents, lubricants, blues Dyes, pigments, fluorescent dyes, ultraviolet absorbers, antioxidants, quenchers, preservatives, antifungal agents, antistatic agents, water-resistant agents for binders, cross-linking agents, etc. for color tone adjustment such as seasoning Various auxiliaries known in the field are added to form a coating liquid.

As a result of further studies, the present inventors have found that when zirconium salts are added to a coating liquid for an intermediate layer containing a xerogel-based porous pigment, the squealing during recording can be further improved. Presumably, the addition of the zirconium salt enhances the structure retention of the intermediate layer and is achieved to reduce the deformation of the base paper upon absorption of the aqueous ink medium.

The zirconium salts added to the coating solution for the intermediate layer include (NH ₄ ) ZrO (CO ₃ ) ₂ and ZrO (CO ₃ )
_{2 · 8H 2 O, ZrO (} OH) Cl · nH 2 O, ZrO
SO ₄ .nH ₂ O, ZrO (NO ₃ ) ₂ .8H ₂ O, Zr
OCO ₃ .nH ₂ O, ZrO (OH) ₂ .nH ₂ O, Z
rO (C ₂ H ₃ O ₂ ) _{2 and the} like can be exemplified.

As the zirconium oxychloride active inorganic polymer, for example, a zirconium salt commercially available from Daiichi Rare Element Chemical Industry Co., Ltd. under the trade name of zircosol ZC-2 is also effective. The active inorganic polymer is a zirconium salt that is preferably used because the effect is remarkable when applied to the present invention.

These zirconium salts are appropriately selected and used, and the amount thereof is generally adjusted within a range of about 1 to 50% by weight of the xerogel-based porous pigment in the coating liquid for the intermediate layer. By the way, if the amount is less than 0.1% by weight, a sufficient action and effect cannot be expected. If the amount exceeds 50% by weight, the ink absorbency may be reduced, and disadvantages such as coloring and discoloration of the receiving layer may occur. There is fear.

The coating liquid for the intermediate layer may be prepared by a known method such as a bar coater, air knife coater, blade coater, rod blade coater, roll coater, brush coater, curtain coater, gravure coater, cast coater, spray device, etc. Using a smearing method, this is also smeared by the usual method, but the coating amount is as long as the recording characteristics such as ink receptivity and storage stability are satisfied,
It is not necessary to increase unnecessarily, and generally 1 to 30 g /
m ² , preferably ² to 8 g / m ² .

The coating liquid for the ink receiving layer is also smeared by a conventional method using the above-mentioned smearing method, and the coating amount is as long as the ink receiving property, the storability and the recording characteristics are satisfied.
Need not be many unnecessary, is generally preferably 1 to 30 g / m ² as dry weight 2 to 10 g / m ² coating,
It is formed.

In the present invention, as the substrate, a material having flatness such as paper, cloth, cellophane, plastic film, metal plate, wood plate, and glass plate is used. Among them, paper itself has a porous structure. It is most preferably used because it has excellent water absorbability, and when the ink receiving layer according to the present invention is formed, it is possible to obtain an ink jet recording paper excellent in recording suitability with a smaller coating amount and also excellent in economy. You. In addition, in order to improve the smear suitability of the coating solution for the intermediate layer on the substrate, use of general surface treatment such as corona discharge treatment, plasma treatment, chemical cleaning treatment, gelatin,
Resin-treated layer of nitrocellulose, polyester, etc./
Alternatively, a known anchor coat layer such as a layer treated with an auxiliary agent such as colloidal silica, a metal-based coupling agent, and isocyanates can be used.

In the above-mentioned base material, paper is generally composed mainly of wood pulp, but various fibrous substances such as synthetic fibers, synthetic pulp, inorganic fibers and the like are appropriately used as needed. , Alkyl ketene dimer, sizing agent represented by alkenyl succinic acid, etc., sulfate band, fixing agent represented by cationic polymer electrolyte, etc., clay, talc,
Calcium carbonate, calcined kaolin, aluminum oxide, aluminum hydroxide, titanium oxide, amorphous silica, urea
Fillers such as formalin resin particles, polyacrylamide polymers, paper strength agents such as starch,
Melamine resin, urea resin, wet paper strength agent represented by polyamide-polyamine-epichlorohydrin resin, etc.,
In addition, drainage agents, dyes for adjusting the color tone such as bluing, pigments, various auxiliary agents such as fluorescent dyes are appropriately selected and internally added, papermaking is performed by various paper machines according to a conventional method, and further starch, if necessary. It is manufactured through a processing step according to a conventional method such as a surface size press processing using an aqueous liquid composed of polyvinyl alcohol, gelatin, a filler and the like, and a smoothing processing using a machine calender or the like.

In addition, these papers have various types and amounts of auxiliaries such as pulp composition, beating conditions, fillers, paper strength agents, internal sizing agents, pH adjusters, surface sizing agents, surface treatment agents and the like. Control, drying conditions, pressurizing conditions, etc., are appropriately selected and controlled for operating conditions according to each paper machine, and are used by controlling the suitability of the base material as a recording material.

The recording material thus obtained can be used as it is, but if necessary, the surface can be smoothed by a conventional method, for example, by passing through a pressurized and / or heated roll nip with a super calender, gloss calender or the like. . If necessary, the surface and / or the back of the recording paper may be subjected to a surface treatment such as an antistatic treatment, a writing suitability and a printability imparting treatment, or an ultraviolet absorbent may be applied to an arbitrary position of the coating layer or the base material. Needless to say, it is also possible to incorporate an auxiliary agent such as an antioxidant to further improve the storability of the recorded image.

[0038]

The present invention will be described in more detail with reference to the following Examples, which, of course, are not intended to limit the scope of the present invention. In the description, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, converted into solid contents, unless otherwise specified.

Example 1 "Formation of Intermediate Layer" Commercially available xerogel-based porosity in water to which 5 parts of a nitrogen-containing water-soluble resin (trade name: Sumireze Resin # 1001, manufactured by Sumitomo Chemical Co., Ltd.) was added. Silica A [pore radius: 89 °, average particle size: 3.5 μm, specific surface area: 35]
0 m ² / g, trade name: Mizukasil P-78A, manufactured by Mizusawa Chemical Co., Ltd.] 85 parts, and xerogel-based porous silica B
[Pore radius: 85 °, average particle size: 6 μm, specific surface area: 3
00 m ² / g, trade name: Syloid # 404, manufactured by Fuji Devison Co., Ltd.] and dispersed therein, modified polyvinyl alcohol [trade name: Kuraray R-Polymer R-11]
30, manufactured by Kuraray Co., Ltd.] as a solution to prepare an intermediate layer coating solution having a solid content of 15%. This coating solution was applied and dried on a base paper made of acidic paper having a basis weight of 64 g / m ² and a Steckigt sizing degree of 2 seconds to a dry weight of 4 g / m ² to form an intermediate layer.

[Preparation of Recording Material] Next, a commercially available xerogel-based porosity was added to water to which 10 parts of a nitrogen-containing water-soluble resin (trade name: Sumireze Resin # 1001, manufactured by Sumitomo Chemical Co., Ltd.) was added. Silica C [pore radius: 40 °, average particle size: 7.
1 μm, specific surface area: 270 m ² / g, trade name: Fine Seal X-60, manufactured by Tokuyama Soda Co., Ltd.]
To this, modified polyvinyl alcohol [trade name: Kuraray R]
-Polymer R-1130, manufactured by Kuraray Co., Ltd.] as a solution, and a fluorescent dye and an antifoaming agent were further added to prepare a coating solution for an ink receiving layer having a solid content of 15%. This coating liquid was applied onto the above-mentioned intermediate layer at a dry weight of 3 g / m 2.
^After smearing and drying to provide an ink receiving layer so that it becomes ² ,
The recording material was obtained by performing a super calendar process.

Comparative Example 1 The procedure of Example 1 was repeated except that no intermediate layer was provided (dry weight of ink receiving layer: 3).
g / m ² ) to obtain a recording material.

Comparative Example 2 In Example 1, no intermediate layer was provided, and the amount of the ink receiving layer applied was 7 g / m ² in terms of dry weight.
A recording material was obtained in the same manner as in Example 1 except that the recording material was changed.

[Comparative Example 3] In Example 1, the coating liquid for the intermediate layer was smear-dried to a dry weight of 4 g / m ² and dried.
A recording material was obtained in the same manner as in Example 1 except that smearing of the receiving layer coating liquid was not performed.

[Comparative Example 4] In Example 1, the coating liquid for the intermediate layer was smear-dried to a dry weight of 7 g / m ² ,
A recording material was obtained in the same manner as in Example 1 except that smearing of the receiving layer coating liquid was not performed.

Example 2 In Example 1, a zirconium oxychloride-based active inorganic polymer was added to the coating solution for the intermediate layer [trade name:
Zircosol ZC-2, manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.]
An ink jet recording paper was obtained in the same manner as in Example 1 except that 3 parts were added.

[Evaluation] The six types of recording materials thus obtained were subjected to a quality comparison test as follows. In addition, as an evaluation machine, an image jet printer (IO-735X type) manufactured by Sharp Corporation was used.

(Ink Acceptability) The dry state of the two-color ink superimposed solid printing portion and the clarity of the printing boundary portion were visually judged. (Clarity) The overprinted portion (green portion) of the cyan and yellow inks was measured with an Ellejo 2000 type colorimeter and was indicated by a C ^* value. (Image quality) The presence or absence and the degree of color unevenness in the green solid printing portion were visually determined. (Bumpiness) Green solid printing was performed on the entire surface, and the degree of unevenness was determined.

(Evaluation) A ... B ... C ... D Excellent Inferior

[0049]

[Table 1]

Example 3 "Formation of Intermediate Layer" Commercially available xerogel-based porosity in water to which 5 parts of a nitrogen-containing water-soluble resin (trade name: Sumireze Resin # 1001, manufactured by Sumitomo Chemical Co., Ltd.) was added. Silica D [pore radius: 89 °, average particle size: 8.0 µm, specific surface area: 36]
5 m ² / g, trade name: Mizukasil P-78D, manufactured by Mizusawa Chemical Co., Ltd.] and modified polyvinyl alcohol [trade name: Kuraray R-Polymer R-113]
0, manufactured by Kuraray Co., Ltd.] and 12 parts of a cation-modified polyvinyl alcohol [trade name: PVA C-118, manufactured by Kuraray Co., Ltd.] as an aqueous binder solution to prepare an intermediate layer coating solution having a solid content of 15%. did. Apply this coating solution with a basis weight of 8
An intermediate layer was formed by applying a dry weight of 4 g / m ² on a base paper made of neutral paper of 4 g / m ² and a Steckigt sizing degree of 7 seconds.

[Preparation of Recording Material] Next, commercially available xerogel-based porosity was added to water to which 20 parts of a nitrogen-containing water-soluble resin (trade name: Sumireze Resin # 1001, manufactured by Sumitomo Chemical Co., Ltd.) was added. Silica E [pore radius: 40 °, average particle size: 2.
6 μm, specific surface area: 270 m ² / g, trade name: Fine Seal X-37, manufactured by Tokuyama Soda Co., Ltd.] 85 parts, and xerogel porous silica F [pore radius: 85 °, average particle size:
12 μm, specific surface area: 300 m ² / g, trade name: Syloid # 620, manufactured by Fuji Devison Co., Ltd.], and modified polyvinyl alcohol [trade name: Kuraray R-Polymer R-1130, Co., Ltd.] Kuraray] 17
Of a binder aqueous solution, a fluorescent dye and an antifoaming agent were further added to prepare an ink receiving layer coating liquid having a solid content concentration of 15%. This coating liquid was smear-dried on the above-mentioned intermediate layer so as to have a dry weight of 4 g / m ² to provide an ink receiving layer, and then subjected to a super calender treatment to obtain a recording material.

Comparative Example 5 The procedure of Example 3 was repeated except that no intermediate layer was provided (dry weight of ink receiving layer: 4).
g / m ² ) to obtain a recording material.

Comparative Example 6 In Example 3, the intermediate layer was not provided, and the amount of the ink receiving layer applied was 8 g / m ² in terms of dry weight.
A recording material was obtained in the same manner as in Example 3 except that the above conditions were adopted.

[Comparative Example 7] In Example 3, the coating solution for the intermediate layer was smear-dried to a dry weight of 4 g / m ² and dried.
A recording material was obtained in the same manner as in Example 3, except that the coating solution for the receiving layer was not smeared.

[Comparative Example 8] In Example 3, the coating solution for the intermediate layer was smear-dried so as to have a dry weight of 8 g / m ² ,
A recording material was obtained in the same manner as in Example 3, except that the coating solution for the receiving layer was not smeared.

Example 4 In Example 3, a zirconium oxychloride-based active inorganic polymer was added to the coating solution for the intermediate layer.
Zircosol ZC-2, manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.]
A recording material was obtained in the same manner as in Example 3, except that 3 parts were added.

Example 5 "Formation of Intermediate Layer" Nitrogen-containing water-soluble resin [trade name: PAS]
J-41, manufactured by Nitto Boseki Co., Ltd.] Commercially available xerogel-based porous silica E [pore radius: 4]
0 °, average particle size: 2.6 μm, specific surface area: 270 m ² /
g, Trade name: Fine Seal X-37, Tokuyama Soda Co., Ltd.
50 parts and xerogel-based porous silica F [pore radius: 85 °, average particle size: 12 µm, specific surface area: 300 m]
² / g, trade name: Syloid # 620, manufactured by Fuji Devison Co., Ltd.], and 50 parts of polyvinyl alcohol [trade name: PVA-110, manufactured by Kuraray Co., Ltd.] as a binder aqueous solution were added thereto. Further, a zirconium acid-based active inorganic polymer [trade name: Zircosol ZC-
2, Daiichi Rare Element Chemical Industry Co., Ltd.] to prepare an intermediate layer coating solution having a solid content of 15%. The coating liquid was smear-dried on a base paper made of acidic paper having a basis weight of 74 g / m ² and a Steckigt sizing degree of 3 seconds so as to have a dry weight of 5 g / m ² .

[Preparation of Recording Material] Next, the coating liquid for the ink receiving layer used in Example 3 was smear-dried to a dry weight of 3 g / m ² to obtain a recording material.

[Evaluation] The seven types of recording materials thus obtained were subjected to a quality comparison test as follows. In addition, as an evaluation machine, an image jet printer (IO-735X type) manufactured by Sharp Corporation was used.

(Ink Acceptability) The dry state of the two-color ink superimposed solid printing portion and the clarity of the printing boundary portion were visually judged. (Clarity) The overprinted portion (green portion) of the cyan and yellow inks was measured with an Ellejo 2000 type colorimeter and was indicated by a C ^* value. (Image quality) The presence or absence and the degree of color unevenness in the green solid printing portion were visually determined. (Bumpiness) Green solid printing was performed on the entire surface, and the degree of unevenness was determined.

(Evaluation) A ... B ... C ... D Excellent Inferior

[0062]

[Table 2]

[0063]

As is clear from the results of Tables 1 and 2, the recording material obtained in the present invention exhibited excellent ink receptivity, excellent clarity, and excellent image quality. In particular, when a zirconium salt was used in combination for the intermediate layer, an excellent improvement effect was also exhibited on the roughness.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-245588 (JP, A) JP-A-4-7189 (JP, A) JP-A-61-3777 (JP, A) JP-A-2- 274587 (JP, A) JP-A-3-133685 (JP, A) JP-A-62-259882 (JP, A) JP-A-63-104878 (JP, A) JP-A-1-258980 (JP, A) JP-A-62-134285 (JP, A) JP-A-62-134287 (JP, A) JP-A-1-249384 (JP, A) JP-A-60-67190 (JP, A) (58) (Int.Cl. ⁷ , DB name) B41M 5/00

Claims (3)

(57) [Claims] 1. A recording material comprising an ink receiving layer having a xerogel-based porous pigment as a main component on a substrate, wherein the ink receiving layer has a pore radius (peak value) measured by a BET method. At least two different xerogel-based porous pigments
A recording material comprising a seed-containing layer and at least one intermediate layer containing a xerogel-based porous pigment between the substrate and the ink receiving layer. 2. A recording material in which an ink receiving layer mainly composed of a xerogel porous pigment is provided on a base material, a pore radius measured by a BET method between the base material and the ink receiving layer. A recording material comprising an intermediate layer containing at least two xerogel-based porous pigments having different peak values. 3. The recording material according to claim 1, wherein the intermediate layer further contains a zirconium salt.