JPH09183265A - Inkjet recording material - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide an inkjet recording material having high gloss, high print density, ink absorbency, and excellent moisture and water resistance. An ink jet recording material having two or more ink receiving layers containing colloidal silica and an adhesive on a support. Further, the above ink jet recording material is disclosed in which an ink receiving layer containing a pigment is provided between a support and two or more layers containing colloidal silica and an adhesive. Further, among the layers containing colloidal silica and the adhesive, the average particle diameter of the uppermost layer (layer far from the support) is 10 n.
Disclosed is the above ink jet recording material, characterized in that the average particle diameter of the layer containing colloidal silica and the adhesive below m to 300 nm is larger than that in the uppermost layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording material, and more particularly to an ink jet recording material having high gloss, ink absorbency, and excellent moisture and water resistance.

[0002]

2. Description of the Related Art The ink jet recording system is a system for recording ink droplets ejected at high speed from a nozzle by adhering it to a recording material, and has features such as easy full colorization and low printing noise. . In this method, since the ink used contains a large amount of solvent, it is necessary to use a large amount of ink in order to obtain a high recording density. In addition, since the ink droplets are continuously ejected, the next droplet is ejected before the first droplet is absorbed, and the ink droplets are likely to be fused to join the ink dots. Therefore, as a recording sheet used in this inkjet recording system, the density of print dots is high,
It is required that the color tone is bright and vivid, and that the ink does not bleed even when printing dots overlap due to fast ink absorption.

In order to solve these problems, a porous pigment is provided on the support as an ink receiving layer to control the color and sharpness which determine the image quality, thereby improving the color reproducibility and the image reproducibility. It was Also, JP-A-62-1117
As disclosed in No. 82, there are attempts to provide two layers of porous particle layers in order to obtain high image quality. In response to the rapid spread of inkjet printers, in the printing field, high gloss glossy photo-like printed matter is required for various publications and applications such as packaging. Especially in the case of color recording, dot shape (round shape), dot sharpness, ink absorption,
There is a strong need for film and coated paper types from the viewpoint of ink acceptability such as fixing speed and ink absorption capacity. When a porous pigment is used, it is necessary to absorb the ink, and thus the size of the pores of the pigment is required, and the pigment is also required to be large accordingly. When the pigment becomes large, not only the smoothness of the surface of the ink receiving layer cannot be obtained, but also the transmission of light can be prevented, the ink receiving layer becomes opaque, and it is difficult to obtain gloss.

Many ink jet recording sheets coated with a resin that absorbs ink by dissolving or swelling for the purpose of imparting gloss are commercially available. However, it is attempted to absorb the ink by dissolving or swelling such a resin. In the present situation, although some gloss can be obtained, the ink drying speed is slow and the water resistance is not good. Therefore, JP-A-1-2
As disclosed in JP-A-37187 and JP-A-1-237188, it has been attempted to balance ink absorbency and water resistance by a two-layer constitution of an ink holding layer and an ink transport layer.
Since the ink holding layer itself has no water resistance, the balance between ink absorbency and water resistance has not yet been fundamentally solved.

As the pigment-containing system, an ink jet recording having an ink receiving layer formed by using a pigment such as silica, alumina, pseudo-boehmite, calcium carbonate, kaolin or the like and a water-soluble polymer such as starch, polyvinyl alcohol or a cellulose derivative as an adhesive agent. Many papers have been reported,
Although the water resistance of these ink receiving layers is excellent, they are generally lacking in smoothness and gloss. For example, Japanese Patent Publication No. 61-60793
JP-A-2-274587 discloses a recording paper in which an ink receiving layer is composed of synthetic silica, colloidal silica and a water-soluble polymer adhesive. However, in order to maintain ink absorbency, it is essential to contain synthetic silica having a relatively large particle size. Synthetic silica generally has a large particle size, and it has been difficult to obtain smoothness and gloss.

In order to obtain smoothness and glossiness, recently, it has been proposed that the ink receiving layer be composed of two or more layers and the upper layer be a gloss developing layer (for example, JP-A-3-215080).
JP-A-3-256785, JP-A-7-89220
JP-A-7-101142, JP-A-7-11733
No. 5, etc.). Colloidal silica or a composite of colloidal silica is used as the main component of these glossy layers. However, since the gloss-developing layer that is generally used is provided for gloss rather than ink absorption, cast treatment (when the gloss-developing layer is in a wet state, pressure-bonded to a heated mirror surface roll to give a mirror gloss finish) Is obtained by
The amount of coating is quite small. A pigment having a large particle size, in which voids are relatively easy to obtain, is used for the lower layer in order to have ink absorbability. With this configuration,
When printing, the ink ejected from the nozzle first hits the gloss developing layer, and most of the ink instantaneously moves to the ink receiving layer, and since the voids in the ink receiving layer are large, the ink immediately spreads and is fixed. Since the voids of the ink receiving layer are large and non-uniform, the periphery of the dots of the obtained ink is jagged and is far from a perfect circle. The image is thereby considerably less sharp.
In addition, since the ink easily spreads, the dots are relatively large. In particular, recently, since ink jet printers with a high linearity of 720 dpi × 720 dpi have begun to spread, when the dots become large, the dots are joined together and a delicate image is formed. I can't get it. Furthermore, since the particles of the ink receiving layer are large and have no transparency, it is impossible to obtain a high print density.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and provide an ink jet recording sheet with higher gloss and higher density. The present invention provides a high-gloss inkjet recording material having a high ink absorption rate, a high printing density, and good water resistance, ink fixability, and printability.

[0008]

An ink receiving layer having a one-layer structure containing colloidal silica and an adhesive (preferably a water-soluble resin) is ideal in terms of gloss, but colloidal silica itself is an ink. Since the ink has no absorbability, the ink is absorbed in a slight gap between the colloidal silica and the water-soluble resin that is the binder. Therefore, a high coating amount (10 g / m ² or more) is indispensable for completely absorbing the ink. However, if the particle size of the colloidal silica used is small, the amount of binder added must be suppressed to a considerably small amount in order to absorb the ink. As a result, when the coating amount is high, the coating layer is cracked, and the desired high-gloss inkjet recording sheet cannot be obtained. On the other hand, if the particle size of the colloidal silica used is large, it is possible to increase the amount of binder added, and it is easy to obtain a high coating amount, but if the particle size is large, the transparency of the coating film decreases and high printing density is obtained. It may be difficult to obtain.

Therefore, as a result of repeated studies in the present invention, the upper layer of the ink receiving layer is a layer containing colloidal silica having a relatively small particle size and an adhesive, and the lower layer is adhesive to a colloidal silica having a relatively large particle size. The above problem can be solved by forming a layer containing an agent (preferably a water-soluble resin). The function of the upper layer is not only to absorb a part of the ink but also to obtain print density and gloss. The lower layer absorbs ink that the upper layer cannot absorb,
By adding more binder than the upper layer, a high coating amount can be realized without causing cracks in the ink receiving layer.

Since the particle size of colloidal silica is much smaller than the particle size of commonly used coating pigments and the distribution is uniform, ink bleeding and spreading are small and the dot size is controlled. Since the lower layer of the present invention is also a colloidal silica-based material, it has the advantages that the voids in the layer are small and uniform, and that round dots are easily obtained. Also, upper and lower 2
Since the layers are both colloidal silica / adhesive, the transparency of the ink receiving layer is relatively good, and high printing density can be obtained. Although the effect of the present invention can be sufficiently obtained with the above-mentioned two layers, when the demand for ink absorption (particularly for solid color solid areas) is considerably high, the above-mentioned two-layer colloidal silica / adhesive which cannot be completely absorbed is further added. It is absorbed by the third layer of colloidal silica / adhesive (preferably a water-soluble resin layer) or another ink absorbing layer. As described above, a printed image with high gloss and clear, delicate and high density can be obtained.

Furthermore, when polyvinyl alcohol is used as the water-soluble resin in the colloidal silica / water-soluble resin layer of the ink jet recording sheet of the present invention, the compatibility between colloidal silica and polyvinyl alcohol is good.
A uniform dispersion coating liquid can be prepared, and a transparent and glossy ink receiving layer can be easily obtained. When a cation-modified colloidal silica is used as the colloidal silica, an ink jet recording sheet having good ink fixability and moisture-resistant storage stability can be obtained. Furthermore, when the ink receiving layer of the present invention is applied on the molding surface to form a film and then transferred onto the support through the intermediate layer, the gloss is increased, and an ink jet recording sheet having high smoothness and high gloss comparable to that of a photograph is obtained. .

The present invention includes, but is not limited to, the following aspects. [1] An ink jet recording material in which two or more ink receiving layers containing colloidal silica and an adhesive are provided on a support.

[2] The ink jet recording material according to claim 1, wherein an ink receiving layer containing a pigment is provided between the support and two or more layers containing the colloidal silica and the adhesive.

[3] Of the layers containing colloidal silica and the adhesive, the average particle diameter of the colloidal silica of the uppermost layer (the layer far from the support) is 10 nm to 300 nm, and the colloidal silica below it is bonded. The ink jet recording material according to [1] or [2], wherein the layer containing the agent has an average particle size of colloidal silica larger than that in the uppermost layer.

[4] At least one of the layers containing colloidal silica and the adhesive is a cationic colloidal silica [1], [2] or [3].
The inkjet recording material described.

[5] The ink receiving layer is formed by coating on the molding surface and then transferred onto a support through an intermediate layer having adhesiveness or tackiness [1],
The inkjet recording material according to [2], [3] or [4].

[6] The ink jet recording material as described in the above item, wherein the content of the adhesive in the layer containing colloidal silica and the adhesive is higher than that of the uppermost layer. [7] The inkjet recording material according to the above item, wherein the adhesive of at least one layer containing colloidal silica and an adhesive is polyvinyl alcohol. [8] The ink jet recording material according to the above items, wherein the ink receiving layer contains a cationic resin.

[9] The intermediate layer is a thermoplastic resin, an adhesive,
The inkjet recording material according to [5], which is at least one selected from pressure-sensitive adhesives. [10] The inkjet recording material according to [5] or [9], wherein the molding surface is a film having a highly smooth surface, laminated paper, glassine paper, inorganic glass, or a metal surface. [11] The inkjet recording material according to [2], wherein an ink receiving layer containing silica or alumina is provided between the support and two or more layers of colloidal silica and a layer containing an adhesive.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises a sheet-shaped support such as paper or film provided with two or more ink receiving layers containing colloidal silica and an adhesive (preferably a water-soluble resin). And containing colloidal silica and adhesive 2
Another pigment-containing ink absorption layer may be further provided between the layer and the support.

In the present invention, examples of the support include films such as cellophane, polyethylene, polypropylene, soft polyvinyl chloride, hard polyvinyl chloride and polyester, fine paper, art paper, coated paper, cast coated paper, Foil paper, kraft paper, polyethylene laminated paper,
Papers such as impregnated paper, vapor-deposited paper, and water-soluble paper, and sheets such as metal foil and synthetic paper are appropriately used.

Next, the ink receiving layer of the present invention will be described in detail. First, the lower layer (closer to the support) containing colloidal silica and adhesive (hereinafter abbreviated as lower layer) in a mode in which the ink receiving layer has at least two layers containing colloidal silica and an adhesive will be described. The lower layer of the present invention comprises colloidal silica and an adhesive, and the average particle diameter (B
The surface area is measured by the ET method, and the average particle size is calculated. Unless otherwise specified, the following average particle diameters of colloidal silica are all measured by this method) is 2
It is adjusted to 0 to 300 nm, preferably 30 to 250 nm. Of course, if necessary, two or more kinds of colloidal silica may be used in combination. The colloidal silica used may be an anion type or a cation type, but it is preferable to use the cation type colloidal silica in consideration of practical use such as high humidity storage stability.

As the adhesive (used as a binder), for example, polyvinyl alcohol, casein, soybean protein, synthetic proteins, starch, water-soluble resins such as cellulose derivatives such as carboxymethyl cellulose and methyl cellulose, styrene-butadiene copolymer, methyl. Conventionally used as coated paper for latex such as conjugated diene-based polymer latex of methacrylate-butadiene copolymer, acrylic-based polymer latex, vinyl-based polymer latex such as ethylene-vinyl acetate copolymer, etc. A known adhesive (binder) is appropriately added and used. Among the adhesives, water-soluble resin is preferable. Polyvinyl alcohol (hereinafter referred to as PVA) is most effective because of its suitability for dispersion with colloidal silica. Further, PVA having a saponification degree of 95% or more and a polymerization degree of 1100 or less is used, or a silicon-containing modified PVA having a polymerization degree of 1100 or less is used.
When used, a uniform colloidal silica / PVA dispersion coating liquid is obtained, and when it is used for coating, a glossy ink receiving layer having relatively good transparency is obtained.

The solid content weight ratio of the colloidal silica and the adhesive is preferably 4/1 to 50/1, more preferably 20 /.
It is adjusted to the range of 3 to 20/1. When the amount of the adhesive is large, the ink absorption speed may be slow, while when the amount of the adhesive is small, the ink receiving layer may be cracked, which is not suitable.
Of course, other pigments may be blended in addition to the colloidal silica and the adhesive, if necessary. For example, amorphous silica, kaolin, clay, calcined clay, zinc oxide, tin oxide, magnesium sulfate, aluminum oxide, aluminum hydroxide, calcium carbonate, satin white, aluminum silicate, smectite, zeolite, magnesium silicate, magnesium carbonate, magnesium oxide. , Diatomaceous earth, styrene-based plastic pigments, urea resin-based plastic pigments, benzoguanamine-based plastic pigments, and other various publicly known pigments used in the general coated paper field are appropriately used. However, in order to maintain the smoothness and transparency of the ink receiving layer, the amount used is preferably 25% or less based on the colloidal silica. The average particle size of the pigment added to the colloidal silica is preferably 2 μm or less.

If desired, a cationic resin may be added to the lower layer of the ink receiving layer of the present invention. Thereby, the ink fixability can be improved. Examples of the cationic resin include polyalkylenepolyamines such as polyethyleneamine and polypropylenepolyamine, or derivatives thereof, acrylic resins having a tertiary amino group or quaternary ammonium group, and diacrylamine.
Although the addition amount of the cationic resin is not particularly limited, Pigment 1
1 to 30 parts by weight, more preferably 5 to 100 parts by weight
It is adjusted in the range of up to 20 parts by weight. In addition, various auxiliaries such as a dispersant, a thickener, a defoaming agent, a coloring agent, an antistatic agent, and a preservative used in the production of general coated paper are appropriately added.

The coating amount of the lower layer is not limited, but is 3 to 60 g.
/ M^Two , Preferably 5 to 40 g / m ^Two Adjust to. Few
If so, the amount of ink absorbed will be small and the effect will be saturated even if it is large
It is meaningless. 15 g / m^Two To obtain high coating weight
In addition to thickening and increasing the concentration of the coating liquid, the coating liquid should be applied twice or more times.
It can also be realized by the cover. Next, the upper layer is explained
I will tell. The upper layer is obtained by coating on the lower layer. Upper layer
The basic structure is the same as the lower layer, but in order to obtain print density
It is preferable that the particle size is smaller than that of the lower layer. Average particle size is 10
nm to 300 nm is preferable, more preferably 20 nm
It is adjusted to the range of 150 nm. Adhesive (binder
-) Content is based on 100 parts by weight of colloidal silica
It is adjusted to the range of 2 to 25 parts by weight. However, contact from the lower layer
The smaller the amount of the adhesive compounded, the more effective. Other required
If necessary, the above-mentioned pigments, water-soluble resins, cationic
Dispersants and thickeners used in the production of resins and general coated paper
Various auxiliaries such as agents, defoamers, colorants, antistatic agents, preservatives, etc.
Is added appropriately.

An ink receiving layer containing colloidal silica and an adhesive may be further provided under the lower layer to absorb the ink in the high density recording portion and improve the absorbing ability. Further, even if the third ink receiving layer provided below the two colloidal silica-containing layers is a general ink absorbing layer, the high ink absorbing speed, high printing density, high gloss, and printing which are the objects of the present invention are obtained. An inkjet recording sheet having good suitability and water resistance can be obtained. From the viewpoint of the ink absorption rate, the pigment-containing layer is more effective than the layer containing only the water-soluble resin as the ink absorbing layer.

Next, the ink absorbing layer will be specifically described. As the pigment used in the ink absorbing layer, various types of pigments publicly known and used in the general coated paper field such as amorphous silica, clay, alumina and smectite are appropriately used. From the viewpoint of print density and the like, silica or alumina is preferably used. Examples of the adhesive (binder) include the above-mentioned adhesives such as PVA, casein, and starch. Although the amount of the adhesive added is not limited, it is adjusted within the range of 5 to 150 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment. Further, the cationic resin (such as amine-based resin) as described above may be contained to improve the ink fixability. The amount of the cationic resin added is adjusted within the range of 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the pigment. In addition, various auxiliaries such as a dispersant, a thickener, an antifoaming agent, a coloring agent, an antistatic agent, and a preservative used in the production of general coated paper are also appropriately added.

The coating amount of the ink absorbing layer is not particularly limited, but it is preferably adjusted to ³ to 30 g / m ² . If it is too small, the ink absorption is insufficient, which is not preferable. on the other hand,
If it is too much, the effect will be saturated and meaningless. As a coating coater for obtaining any ink receiving layer, a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater,
Various known coating devices such as a lip coater and a curtain coater can be used.

The ink receiving layer can be formed on the support by a coating device. In addition, an ink receiving layer is formed on the molding surface, an intermediate layer having adhesiveness or tackiness is provided on the support (or the ink receiving layer), the intermediate layer and the ink receiving layer (or the support) are adhered, and only the molding surface is formed. The ink receiving layer can be provided by peeling off. When the ink receiving layer is formed using the molding surface in this manner, more excellent gloss can be obtained. Next, only the case where the ink receiving layer is applied to the molding surface to form a film, the support is provided with an intermediate layer, the ink receiving layer and the intermediate layer are laminated so as to face each other, and the molding surface is peeled off, The same applies when an intermediate layer is provided on the ink receiving layer.

As a bonding method, a laminating method (a known laminating method such as a dry laminating method, a wet laminating method, a hot melt laminating method, and an extrusion laminating method can be mentioned) is effective. In the wet laminating, dry laminating, and hot melt laminating methods, a thermoplastic resin or an adhesive is applied to the support to form an intermediate layer, and the intermediate layer and the ink receiving layer are bonded so that they face each other Then, the desired ink jet recording sheet is obtained. In the extrusion laminating method, a thermoplastic resin such as polyethylene which is heated and melted in a melt extruder at 280 to 320 ° C. (a similar method is used when other resin is used) is flowed on the surface of the support, The desired ink jet recording sheet is obtained by sticking the molding surface having the ink receiving layer, cooling and pressure bonding with a cooling roll, and peeling off the molding surface.

When a pressure-sensitive adhesive is used as the intermediate layer, a publicly known coating method such as a bar coater, roll coater, lip coater or the like is used, and after coating and drying the support, the ink-receiving layer and the ink-receiving layer are laminated together. After combining, the molding surface can be peeled off to obtain a desired inkjet recording sheet. The coating amount of the intermediate layer is not particularly limited as long as it can bond the ink receiving layer and the support, but it is ² to 50 g / m ² when any of the thermoplastic resin, the adhesive and the pressure sensitive adhesive is used. To be adjusted. If the coating amount is small, it is difficult to obtain a sufficient adhesive strength, while if it is large, the effect is saturated and is meaningless.

Examples of the thermoplastic resin used for the intermediate layer include ethyl cellulose, vinyl acetate resin and its derivatives, polyethylene, ethylene vinyl acetate copolymer, polyvinyl alcohol, acrylic resin, polystyrene and its copolymer, polyisobutylene, Various publicly known and publicly known thermoplastic resins such as hydrocarbon resins, polypropylene, polyamide resins and polyester resins can be mentioned. Further, as the adhesive, a thermosetting resin such as urea resin, phenol resin, epoxy resin, polyisocyanate resin, polyvinyl acetal / phenol resin, rubber / phenol resin, composite polymer type adhesive such as epoxy / nylon resin, latex Rubber-based adhesive such as type rubber-based, starch,
Examples include various publicly known adhesives such as hydrophilic natural polymer adhesives such as glue and casein. Examples of the pressure sensitive adhesive include various publicly known pressure sensitive adhesives such as a solvent type pressure sensitive adhesive, an emulsion type pressure sensitive adhesive, a hot melt type pressure sensitive adhesive and a delayed type pressure sensitive adhesive.

As the material used for the molding surface, films such as cellophane, polyethylene, polypropylene, soft polyvinyl chloride, hard polyvinyl chloride, polyester having smooth surface, polyethylene laminated paper, glassine paper, impregnated paper Paper such as vapor-deposited paper, sheets such as metal foil and synthetic paper, and plates having a smooth surface such as inorganic glass, metal and plastic are appropriately used. Especially,
Polymer films (polyethylene, polypropylene, polyester, etc.), polyethylene laminated paper, glassine paper, and inorganic glass are preferable from the viewpoints of coating suitability and peeling suitability between the molding surface and the ink receiving layer.

Even if the molding surface is left untreated, in order to improve the peeling property between the molding surface and the ink receiving layer, a resin having a peeling property such as silicone or fluororesin is coated on the coating surface of the molding surface. Can also be used. In order to improve the printability, it is also effective to subject the molding surface to surface hydrophilic treatment by corona discharge or plasma treatment. The molding surface is preferably smooth, and the surface roughness Ra (JIS B 0601-198).
2) is preferably 1 μm or less, more preferably 0.1 μm
m or less.

The coating step of the ink receiving layer when transferring to the support through the intermediate layer is the reverse of the coating step when the ink receiving layer is directly provided on the support. That is, the upper surface of the ink receiving layer is first coated on the molding surface, and then the lower layer is coated thereon. The water content of the ink receiving layer when transferred to the support via the intermediate layer is preferably 20% or less, more preferably 10% or less. When the water content is high, the adhesive force between the molding surface and the ink receiving layer becomes strong, the layers of the ink receiving layer are peeled off when the molding surface is peeled off, the ink receiving layer remains on the molding surface, and the desired inkjet recording material is obtained. It may not be obtained.

The ink used in the ink jet recording method of the present invention contains a dye for forming an image and a liquid medium for dissolving or dispersing the dye as essential components, and if necessary, various dispersants and interfaces. It is prepared by adding an activator, a viscosity adjusting agent, a specific resistance adjusting agent, a pH adjusting agent, an antifungal agent, a dissolution or dispersion stabilizer of a recording agent, and the like. Recording agents used in ink include direct dyes, acid dyes, basic dyes,
Examples thereof include reactive dyes, food dyes, disperse dyes, oil dyes and various pigments, and conventionally known dyes can be used without particular limitation. The content of such a dye is determined depending on the type of liquid medium component, the properties required for the ink, etc., but in the case of the ink of the present invention, the formulation as in the conventional ink, that is, There is no particular problem when used in a proportion of about 0.1 to 20% by weight.

As the solvent of the ink used in the present invention, water and various water-soluble organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol,
C1-C4 alkyl alcohols such as isopropyl alcohol, n-butyl alcohol and isobutyl alcohol, ketones or ketone alcohols such as acetone and diacetone alcohol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, , Propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol, diethylene glycol, and other alkylene groups having 2 to 6 alkylene groups, amides such as dimethylformamide, ethers such as tetrahydrofuran, glycerin, Polyhydric alcohols such as ethylene glycol methyl ether, diethylene glycol methyl (ethyl) ether, and triethylene glycol monomethyl ether Such as a lower alkyl ether of Le and the like.

[0038]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
Further, unless otherwise specified, parts and% in the examples are solid contents excluding water and represent parts by weight and% by weight, respectively. The inkjet recording sheets obtained in the present invention were all processed by a super calendar (linear pressure: 20 Kg / cm) and then used for evaluation.

Example 1 Cation-modified colloidal silica having an average particle diameter of 85 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-Z)
L) 100 parts, silicon-containing modified PVA (Kuraray Co., Ltd., trade name: R-2105, saponification degree: 98.5%, polymerization degree:
500) 15% aqueous solution mixed with 15 parts by a Mayer bar so as to have a coating amount of 15 g / m ² commercially available printing coated paper (manufactured by Shin Oji Co., Ltd., trade name: OK coat, 127.
9 g / m ² ) was coated on one side of the coated paper by the extrusion laminating method with 15 μm of polyethylene (hereinafter simply referred to as “laminated coated paper”) and dried.

Next, 100 parts of a cation-modified colloidal silica having an average particle diameter of 45 nm (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex AK-XL) was added to a silicon-containing modified PVA.
(Kuraray Co., Ltd., trade name: R-2105) A 15% aqueous solution mixed with 8 parts was coated and dried on the above coating layer with a Meyer bar so that the coating amount was 10 g / m ^2, and the inkjet of the present invention. A recording body was manufactured.

Example 2 Cation-modified colloidal silica having an average particle size of 85 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-Z)
L) A 15% aqueous solution prepared by mixing 100 parts of silicon-containing modified PVA (Kuraray Co., Ltd., trade name: R-2105) with a Mayer bar to give a coating amount of 15 g / m ² as in Example 1. The same laminated coated paper was coated and dried on the laminated surface. Next, 100 parts of cation-modified colloidal silica having an average particle diameter of 65 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-YL) and 10 parts of silicon-containing modified PVA (manufactured by Kuraray Co., Ltd., trade name: R-2105). Mixed 15
% Aqueous solution was applied onto the above coating layer with a Mayer bar so that the coating amount was 10 g / m ^2, and dried to produce the inkjet recording material of the present invention.

Example 3 Cation-modified colloidal silica having an average particle size of 150 nm (manufactured by Nissan Kagaku Co., Ltd., Snowtex MP-2040A)
K) 100 parts, PVA (Kuraray Co., Ltd., trade name: PVA
-105, saponification degree: 98.5%, polymerization degree: 500) 2
A 15% aqueous solution mixed with 0 parts was applied to a laminated surface of the same laminated coated paper as described above with a Mayer bar so that the coating amount was 10 g / m ² and dried. Next, average particle size 8
5 nm anionic colloidal silica (Nissan Chemical Co.,
Product name: Snowtex ZL) 100 copies, PVA
(Kuraray Co., Ltd., trade name: PVA-105) A 15% aqueous solution prepared by mixing 15 parts with a Mayer bar has a coating amount of 10 g / m 2.
It was coated and dried on the coating layer to be ^2. further,
On this coating layer, 100 parts of anionic colloidal silica having an average particle diameter of 65 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex YL) and PVA (manufactured by Kuraray Co., Ltd., trade name: P)
VA-105) 15% aqueous solution mixed with 10 parts was coated and dried with a Meyer bar so that the coating amount was 5 g / m ^2, and
The inkjet recording material of the present invention was manufactured.

Example 4 100 parts of amorphous silica (manufactured by Tokuyama Corporation, trade name: Fineseal X-45, average particle size: 4.5 μ) was added to PVA.
(Kuraray, trade name: PVA-117 (saponification degree: 9
8.5%, degree of polymerization: 1750)) 30 parts, and a 15% aqueous solution in which a cationic resin (Sumitomo Chemical Co., Ltd., trade name: SR-1001) 15 parts was mixed, and the coating amount was 1 with a Mayer bar.
It was coated and dried on the laminated surface of the same laminated coated paper as described above so as to obtain 0 g / m ² . Next, average particle size 85
nm cation-modified colloidal silica (Nissan Chemical Co.,
Trade name: Snowtex AK-ZL) 100 parts, silicon-containing modified PVA (Kuraray Co., Ltd., trade name: R-210)
5) A 15% aqueous solution mixed with 15 parts was applied to the above coating layer with a Meyer bar so that the coating amount was 10 g / m ^2, and dried. Further, on this coating layer, an average particle diameter of 45 nm Cation-modified colloidal silica (Nissan Chemical Co., Ltd., trade name: Snowtex AK-XL) 100 parts, silicon-containing modified PVA (Kuraray Co., Ltd., trade name: R-2105) 8
15% aqueous solution mixed with 1 part with a Mayer bar to apply a coating amount of 5
It was coated and dried so as to be g / m ² to produce the inkjet recording material of the present invention.

Example 5 Amorphous silica in Example 4 was replaced with alumina (manufactured by Sumitomo Chemical Co., Ltd.,
An ink jet recording material of the present invention was manufactured in the same manner as in Example 4 except that the trade name: AKP-G015, average particle diameter: 2.5 μ) was changed.

Example 6 Chain-like anionic colloidal silica (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex UP, average particle size: 40 to 300 n)
m) A 15% aqueous solution prepared by mixing 100 parts of 20 parts of silicon-containing modified PVA (Kuraray Co., Ltd., trade name: R-2105) with a Mayer bar so that the coating amount becomes 15 g / m ² The laminated surface of the coated paper was coated and dried. Next, a cation-modified colloidal silica having an average particle diameter of 45 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-
XL) 100 parts, silicon-containing modified PVA (Kuraray Co.,
Trade name: R-2105) A 15% aqueous solution mixed with 8 parts was coated on the above coating layer with a Meyer bar so that the coating amount was 10 g / m ^2, and dried to produce an inkjet recording material of the present invention. .

Example 7 Cation-modified colloidal silica having an average particle diameter of 85 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-Z)
L) 100 parts by weight of hydroxypropylmethyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: METOLOSE 60SH)
A 15% aqueous solution prepared by mixing 20 parts was applied to the laminated surface of the laminated coated paper with a Mayer bar so that the coated amount was 15 g / m ^2, and dried. Next, 100 parts of cation-modified colloidal silica having an average particle diameter of 45 nm (Nissan Chemical Co., Ltd., trade name: Snowtex AK-XL) and 10 parts of hydroxypropylmethyl cellulose (Shin-Etsu Chemical Co., Ltd., trade name: Metroze 60SH). 15% mixed
The aqueous solution was applied onto the above coating layer with a Meyer bar so that the coating amount was 10 g / m ^2, and dried to produce an inkjet recording material of the present invention.

Example 8 Cation-modified colloidal silica having an average particle diameter of 45 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-X)
L) A 15% aqueous solution prepared by mixing 100 parts of silicon-containing modified PVA (manufactured by Kuraray Co., Ltd., trade name: R-2105) with a Mayer bar was used as a molding surface with a coating amount of 10 g / m ^2. Coated PET film (manufactured by Toray Industries, Inc., 75 μ, trade name: Lumirror T, surface roughness Ra = 0.02 μm) and dried. Next, an average particle size of 85 nm was formed on the coating layer.
100 parts of cation-modified colloidal silica (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-ZL) and silicon-containing modified PVA (manufactured by Kuraray Co., Ltd., trade name: R-2105) 1
A 15% aqueous solution prepared by mixing 5 parts was coated and dried with a Meyer bar so that the coating amount was 15 g / m ² . Next, as a support, commercially available coated paper (manufactured by Shin Oji Co., Ltd., trade name: O
Polyethylene (trade name: Mitsubishi Polyethylene LD manufactured by Mitsubishi Chemical Co., Ltd.) melt liquid (using K-coat, 127.9 g / m ² ) by a melt extrusion coating method (extrude laminating method) while corona discharge on one side. (Solution temperature: 280 to 320 ° C.) is applied to the corona discharge surface of the coated paper so that the coating layer is 30 μ, and the polyethylene resin layer in a molten state and the ink receiving layer are laminated so as to face each other. It was cooled and pressure bonded by a cooling roll. Then P
The ET film was peeled off to manufacture the inkjet recording material of the present invention.

Example 9 Cation-modified colloidal silica having an average particle size of 65 nm
(Nissan Chemical Co., Ltd., trade name: Snowtex AK-Y
L) 100 parts with silicon-containing modified PVA (Kuraray Co., Ltd.
Product name: R-2105) A 15% aqueous solution prepared by mixing 10 parts
Coating amount is 5g / m with Mayer bar^Two Molded surface so that
PET film to be used as (Toray, 75μ, quotient
Product name: Lumirror T, surface roughness Ra = 0.02 μm)
It was dried. Next, an average particle size of 85 nm was formed on the coating layer.
Cation-modified colloidal silica (manufactured by Nissan Chemical Co., Ltd.
Name: Snowtex AK-ZL) 100 parts with silicon
Modified PVA (Kuraray Co., Ltd., trade name: R-2105) 1
A 15% aqueous solution mixed with 5 parts is applied with a Mayer bar to
10g / m^Two Was applied and dried. In addition,
Amorphous silica (manufactured by Tokuyama Corporation, product name:
Inseal X-45, average particle size: 4.5μ) 100 parts
And PVA (Kuraray Co., Ltd., trade name: PVA-117) 3
0 parts, cationic resin (Sumitomo Chemical Co., Ltd., trade name: SR-1
001) 15% aqueous solution mixed with 15 parts
The coating amount is 10 g / m ^Two Apply and dry
Was.

Next, as a support, a commercially available coated paper (manufactured by Shin-Oji Co., Ltd., trade name: OK coat, 127.9 g / m 2) is used.
Polyethylene (Mitsubishi Chemical Co., Ltd., trade name: Mitsubishi Polyethylene LD) melt solution (solution temperature: 280-320 ° C.) by melt extrusion coating method (extrusion lamination method) while corona discharge on one side using ² ).
Was coated on the corona discharge surface of the coated paper so that the coating layer had a thickness of 30 μm, and the polyethylene resin layer in a molten state and the ink receiving layer were laminated so as to face each other, and cooled and pressure-bonded by a cooling roll. Subsequently, the PET film was peeled off to manufacture the inkjet recording material of the present invention.

Comparative Example 1 Cation-modified colloidal silica having an average particle diameter of 45 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-X)
L) 100 parts, PVA (Kuraray, trade name: PVA
-105) A 15% aqueous solution prepared by mixing 8 parts was coated on a laminated surface of a laminated coated paper with a Mayer bar so as to have a coating amount of 10 g / m ^2, and dried to produce an inkjet recording material.

Comparative Example 2 Cation-modified colloidal silica having an average particle diameter of 45 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-X)
L) 100 parts, PVA (Kuraray, trade name: PVA
-105) A 15% aqueous solution prepared by mixing 8 parts was coated on a laminated surface of a laminated coated paper with a Mayer bar so as to have a coating amount of 25 g / m ^2, and dried to produce an inkjet recording material.

Comparative Example 3 Cation-modified colloidal silica having an average particle diameter of 150 nm (manufactured by Nissan Kagaku Co., Ltd., Snowtex MP-2040A)
K) 100 parts, PVA (Kuraray Co., Ltd., trade name: PVA
-105) A 15% aqueous solution mixed with 20 parts was applied to the laminated surface of the laminated coated paper with a Mayer bar so that the coating amount was 25 g / m ^2, and dried to produce an inkjet recording material.

Comparative Example 4 Cation-modified colloidal silica having an average particle diameter of 45 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-X)
L) 50 parts, cation-modified colloidal silica having an average particle diameter of 85 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex)
AK-ZL) 50 parts, PVA (Kuraray Co., Ltd., trade name: P
A 15% aqueous solution prepared by mixing 10 parts of VA-105) was applied to the laminated surface of the laminated coated paper with a Meyer bar so that the coating amount was 25 g / m ^2, and dried to produce an inkjet recording sheet.

Comparative Example 5 PVA was added to 100 parts of amorphous silica (manufactured by Tokuyama Corporation, trade name: Fineseal X-45, average particle size: 4.5 μ).
(Kuraray Co., Ltd., trade name: PVA-117) 30 parts, cationic resin (Sumitomo Chemical Co., Ltd., trade name: SR-1001)
A 15% aqueous solution prepared by mixing 15 parts was applied to the laminated surface of the laminated coated paper with a Mayer bar so that the coated amount was 15 g / m ² and dried. Next, a gloss-developing layer was coated on the surface of this coating layer. The gloss-developing layer was obtained by applying a cast treatment after coating the surface of the coating layer. The cast process is
The coating liquid for the gloss-developing layer was applied to the surface of the above-mentioned coating layer, and after 2 seconds, the coating liquid was pressure-bonded to a mirror-finished roll heated to a surface temperature of 90 ° C. and dried to perform the treatment. To 100 parts of cation-modified colloidal silica having an average particle diameter of 65 nm (manufactured by Nissan Kagaku Co., Ltd., trade name: Snowtex AK-XL), 15 parts of PVA (manufactured by Kuraray Co., Ltd., trade name: PVA-105) and 3 parts of potassium oleate. The mixed 10% aqueous solution was provided on the surface of the coating layer by a cast treatment method by a roll coater so that the coating amount (dry) was 3 g / m ² to obtain a gloss expressing layer,
An inkjet recording sheet was manufactured.

Comparative Example 6 Commercially available strong glossy paper for ink jet recording having a coating layer containing alumina, silica and PVA as main components (supplier: CA
NON, trademark: GP-101) was used. Comparative Example 7 Commercially available strong gloss sheet for inkjet recording having a coating layer containing PVA as a main component (supplier: CANON, trademark:
HG-101) was used.

[Evaluation Method] Examples 1 to 9 and Comparative Examples 1 to 7
The water resistance, glossiness, and water absorption of the inkjet recording paper sheet obtained in 1. were evaluated by the methods described below. Regarding the glossiness and the water absorption of the ink, the glossiness, the ink absorbency, and the print density of the solid portion when recording with a commercially available inkjet printer (trade name: BJC-400J, manufactured by CANON) are shown.

[Glossiness] JIS-Z for solid parts of black, yellow, magenta and cyan inks
-8714 method (incident angle 60, specular gloss of 20 degrees)
In accordance with the above, measurement was performed with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.) and the measured values of 5 times were averaged. [Water resistance] Water droplets were dropped on an ink jet recording sheet, and after 30 minutes, the water droplets were wiped off, and the portion immersed in the water droplets was rubbed with a hand to evaluate the water resistance in four steps. (A: No change was observed in the ink receiving layer. A: The ink receiving layer was slightly removed. B: The ink receiving layer was partially removed.
X: The ink receiving layer was completely removed. )

[Ink Absorbency] The ink absorbency is evaluated as follows.
Immediately after printing, a high-quality paper is stuck to the printed surface every 5 seconds, and it is observed whether the ink is transferred to the high-quality paper.
Measure the time until no transfer occurs at all. The measured number of seconds was evaluated in four stages (⊚: 5 seconds or less, ◯: 5 to 10 seconds,
(Triangle | delta: 10-30 seconds, x: 30 seconds or more). If the time until the ink dries is 10 seconds or less, the ink absorbency is excellent. [Printing Density] The printing density of the solid black portion was measured using a Macbeth reflection densitometer (Macbeth, RD-920).
The numbers shown in the table are average values of 5 measurements.

[Cracks of coating film] The surface of the ink receiving layer was observed with an optical microscope (100 times magnification). (⊚: No cracks are observed on the surface, ○: Partial cracks occur on the surface, and the average length of the cracks is 0.1 mm
Hereinafter, Δ: a crack is partially generated on the surface, the average length of the crack is 0.1 to 1 mm, ×: crack is generated on the entire surface, and the average length of the crack is 1 mm or more)

[0060]

[Table 1]

From the results shown in Table 1, when an ink receiving layer containing colloidal silica and an adhesive was provided on a support, 1
When only one layer is coated, the ink absorbency, print density and cracks on the surface of the coating film cannot be balanced (Comparative Examples 1 to 4), but by providing two or more ink receiving layers containing colloidal silica and an adhesive. The above problems can be solved (Example). Further, when the particle size of the colloidal silica in the upper layers from Examples 1 to 3 is changed, the print density and the cracked state of the surface coating film are greatly changed. When the particle size of the upper layer is small, the print density is easily obtained, but slight cracks may occur on the surface of the coating layer (Example 1). On the other hand, when the particle size is large, the print density is slightly lowered, but cracks on the surface of the coating layer are completely eliminated (Examples 2 and 3). The ink jet recording sheet obtained by coating the ink-receiving layer on the molding surface to form a film, then transferring it onto the support through the intermediate layer and peeling off the molding surface has particularly excellent surface gloss (Example 8). , 9).

[0062]

As is apparent from Table 1, the ink jet recording sheet obtained by the constitution of the present invention has a water resistance,
Good ink absorption and high gloss after receiving ink.
It has a high print density. The inkjet recording material of the present invention has high gloss and has excellent inkjet recording (printing) suitability, high printing density, and moisture resistance / water resistance.

Claims (5)

[Claims] 1. An ink jet recording material comprising a support having two or more ink receiving layers containing colloidal silica and an adhesive. 2. The ink jet recording material according to claim 1, wherein an ink receiving layer containing a pigment is provided between the support and two or more layers containing colloidal silica and an adhesive. 3. An average particle diameter of colloidal silica of the uppermost layer (a layer far from the support) among layers containing colloidal silica and an adhesive is from 10 nm to 300 nm, and colloidal silica and an adhesive below the average particle size. The inkjet recording material according to claim 1 or 2, wherein an average particle diameter of the colloidal silica in the layer containing is larger than that in the uppermost layer. 4. The colloidal silica of at least one of the layers containing colloidal silica and an adhesive is a cationic colloidal silica.
The inkjet recording material described. 5. The ink receiving layer is formed by coating on the molding surface, and then transferred onto a support through an intermediate layer having adhesiveness or tackiness. Three
Alternatively, the inkjet recording material according to claim 4.