JPH09267549A - Recording medium, method for manufacturing recording medium, inkjet recording medium, and inkjet recorded matter - Google Patents

Abstract

(57) [PROBLEMS] To provide a nonwoven fabric capable of high-concentration and high-quality inkjet recording and having excellent water resistance of the obtained image. SOLUTION: A recording medium characterized by forming an ink receiving layer containing at least an alumina hydrate on the surface and inside of a non-woven fabric constituted by accumulating a large number of continuous filaments, and a manufacturing method thereof. Inkjet recording medium and inkjet recorded matter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium suitable for use in an ink jet recording system in which ink is ejected as droplets for recording, and more specifically, a recording medium having a specific ink receiving layer, The present invention relates to a recording medium manufacturing method, an inkjet recording medium, and an inkjet recorded product. These recording media and recorded materials are
It is preferably used for posters, stickers, labels, displays, cut letters, and the like.

[0002]

2. Description of the Related Art Ink jet recording is a system in which minute droplets of ink are ejected and adhered to a recording medium such as paper according to various operating principles to record images, characters, etc. It has features such as easy multicoloring, high flexibility in recording patterns, and no need for development-fixing. It is rapidly popularized in recording methods such as various figures including characters and color images, and various other uses. are doing. In response to this, not only high-speed absorption of ink, high absorption capacity, high-density printing and improvement of image quality, but also water resistance of printed matter have been required for recording media, especially paper. .

By the way, in recent years, since nonwoven fabrics have excellent characteristics not found in paper such as bulkiness, softness, tear resistance, burst resistance, tensile strength and wet strength, posters and displays have been developed. It is widely used as a material for packaging materials and bags. In particular, the non-woven fabric has a feature that it returns to its original state when dried even if it gets wet with water, the waviness (cockling) of the paper surface as seen in paper does not occur, and the hand does not change. The reason for this is that ordinary paper is made only from pulp that is fibrillated by beating in water, whereas chemical fibers and synthetic fibers are used in the manufacture of non-woven fabrics, and these continuous filaments are made into sheets. This is because it has a structure that is integrated like a circle.

In general, non-woven fabrics used as materials for posters, displays, wrapping materials, bags and the like have the wet strength and dimensional stability, which are drawbacks of pulp, by mixing hydrophobic synthetic fibers with the pulp. Not only is it improved, but it also has bulkiness and softness, giving it features not found in paper. For this reason, even if a nonwoven fabric is used as an inkjet recording medium, high-density printing cannot be performed and only low-quality images can be obtained due to the low absorption of the inkjet water-based ink. Further, the water resistance of the obtained image is poor, and when water adheres to the printed matter, the image blurs and deteriorates.

Further, in the method of printing that has been conventionally performed when forming an image on a non-woven fabric, a master plate must be prepared for each single color, which increases the manufacturing cost. Therefore, the unit price cannot be reduced unless a large number of products with the same design are produced, and it is difficult to deal with the case where it is desired to obtain a printed matter of a small number of copies or a small lot.

[0006]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a nonwoven fabric capable of high density and high quality ink jet recording and having excellent water resistance of the obtained image. I am trying. As a result, it is possible to obtain a low-cost non-woven printed matter of a small number of copies and a small number of lots, which was difficult with conventional printing.

[0007]

That is, according to the present invention, an ink receiving layer containing at least an alumina hydrate is formed on the surface and inside of a non-woven fabric constituted by accumulating a large number of continuous filaments. A recording medium characterized by
The manufacturing method, an inkjet recording medium, and an inkjet recorded product.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments of the present invention. FIG. 1 shows a schematic sectional view of an example of the recording medium of the present invention. In FIG. 1, 1 is an ink receiving layer and 2 is a nonwoven fabric which is a base material. Ink receiving layer 1
Is for absorbing water-based ink in order to form an image by an inkjet method, for example. The ink receiving layer 1 can be formed by coating and / or impregnating a non-woven fabric with a coating liquid containing alumina hydrate as a pigment. Therefore, the ink receiving layer 1 is formed not only on the surface of the non-woven fabric 2 which is the base material, but also on the inside thereof, and the boundary between the ink receiving layer 1 impregnated with the coating liquid and the base material 2 not impregnated with the coating liquid is not always required. Not clear.

As the substrate 2, a structure in which continuous filaments, which are generally called non-woven fabric, are used, and there are wet non-woven fabric and dry non-woven fabric depending on the manufacturing method.
Wet non-woven fabric is made by dispersing fibers in water and making them with a net.
It is produced by a so-called papermaking method or the like, which is dried. The dry non-woven fabric is formed by binding fibers formed by a spinning machine or the like with a resin binder without taking a weaving step.

2 and 3 are schematic cross-sectional views of another embodiment of the recording medium of the present invention. For example, image formation by an ink jet system can be performed on both sides thereof. FIG.
Shows that the ink receiving layer described in FIG. 1 is provided on both sides. That is, the ink receiving layer 1a and the ink receiving layer 1b are provided on both surfaces of the substrate 2, respectively. In FIG. 3, the ink receiving layer 1c is formed by impregnating the entire area of the base material with the coating liquid.

Next, the components of the coating liquid for forming the ink receiving layer by coating and / or impregnating the non-woven fabric as the base material will be described. The alumina hydrate, which is a component of the coating liquid used for forming the ink receiving layer of the recording medium of the present invention, is obtained from so-called amorphous alumina hydrate which is X-ray amorphous. Those are preferable. Among them, the amorphous alumina hydrate preferably used in the present invention has an initial particle size of 20 to 30Å and a chemical composition of Al ₂ O ₃ ·.
3H ₂ O.

This amorphous alumina hydrate is chemically unstable and forms a Cα amorphous gel which easily dissolves in an acid or an alkali, and becomes a Cβ gel in a neutral or weak alkaline aqueous solution and / or by heating. And changes. Amorphous alumina hydrate having such properties is called boehmite gel, and its composition is considered to be Al ₂ O ₃ .1.0 to 2.0H ₂ O, which is clearly crystalline boehmite. different. Amorphous alumina hydrate having such properties has a half-value width larger than that of crystalline boehmite in the X-ray diffraction pattern and is called pseudo-boehmite. In addition, such pseudo-boehmite is a compound with low crystallinity, and is described by Rocek et al. (Collect.Czech.Che.
m.Commun., Vol. 56, 1253-1262, 1991), the composition is considered to be Al ₂ O ₃ .xH ₂ O (1.0 <x <2.0).

The reason why the amorphous alumina hydrate having such properties, that is, the pseudo-boehmite here has high ink receptivity, is that its pore radius and pore size distribution are very suitable for ink reception. It is believed to be in the fact that it is in range. The pore size distribution of pseudo-boehmite has two or more maximums. The relatively large pores absorb the solvent component in the ink, and the relatively small pores adsorb the dye in the ink. One of the maximum pore size distributions of pseudo-boehmite is 100
It is preferably Å or less, more preferably 10 to 60Å. The other maximum preferably has a pore radius of 100 to 200 °.

In a recording medium using such an alumina hydrate, for example, one of the alumina hydrates has a positive charge, so that the dye having a negative charge in the ink is well fixed and the color is developed. The second is that there are no problems such as brown discoloration and light resistance of the black ink image that have been conventionally caused by using silica compounds, and the third is the image quality. Particularly, it has advantages such as being preferable as compared with the conventional recording medium in terms of improvement of image quality in a full-color image.

On the other hand, so-called plain paper and conventional ink jet coated paper used in general copying machines contain clay, talc, calcium carbonate, kaolin, etc. as inorganic fillers. These have low ink receptivity because they do not have a pore radius and a pore size distribution suitable for ink reception such as alumina hydrate, especially pseudo-boehmite. Further, since these fillers do not have a positive charge or have a negative charge, fixing of the dye having a negative charge in the ink is poor, and only an image with poor color development can be obtained.

The BET specific surface area of the alumina hydrate is preferably in the range of 60 to 300 m ² / g. When the BET specific surface area is larger than the above range, it becomes impossible to sufficiently adsorb and fix the dye in the ink by deviating to the larger pore size distribution, and when it is smaller than the above range, the ink receiving layer is formed. In order to achieve this, the pigment in the coating liquid cannot be coated with good dispersion, and it tends to be difficult to control the pore size distribution. The BET pore volume of the alumina hydrate is 0.2 to
The range of 0.9 ml / g is preferable. If it is less than the above range, the absorbability of the ink is slightly deteriorated, and if it is more than the above range, powder falling tends to occur.

As the alumina hydrate used in the present invention, a metal oxide containing, for example, titanium dioxide may be used. When titanium dioxide is contained, both the dispersibility and the adsorption of the dye in the ink, which have been difficult in the past, can be further improved as compared with the case where only alumina hydrate is used. The content ratio of titanium dioxide is preferably 0.01 to 1.00% by weight of alumina hydrate, and more preferably 0.13 to 1.00% by weight. Further, the titanium dioxide preferably has a valence of titanium atoms of +4.

Further, the coating liquid for forming the ink receiving layer of the recording medium of the present invention may contain a quaternary ammonium compound as a waterproofing agent. Examples of the quaternary ammonium compound include compounds represented by the following general formula (I)
A polyallylamine derivative represented by can be used. (In the above formula, x ⁻ is Br ⁻ , Cr ⁻ , I ⁻ , HOSO ₃ ⁻ , CH.
₃ OSO ₃ ⁻ or C ₂ H ₅ OSO ₃ ⁻ , and n is 5 to 1
Represents a number of 10,000. )

The polyallylamine derivative represented by the general formula (I) according to the present invention is, for example, obtained in the form of a hydrochloride through the following steps, or in a neutralized form or a mono-form. There are copolymers of allylamine and diallylamine. Specifically, from Nitto Boseki Co., Ltd., PAA-15, PAA
-15B, PAA-10C, PAA-HCl-3L, P
AA-HCl-10L, PAA-HCl-3S, PAA
Commercially available under the trade names of -HCl-10S and PAA-11D0-HCl.

Further, as a quaternary ammonium compound,
A quaternary ammonium salt type water-soluble resin represented by the following general formula (II) can be used. The quaternary ammonium salt type water-soluble resin represented by the general formula (II) is commercially available from Nagase Chemicals Co., Ltd. under the trade name of Wytex.

Further, the coating liquid for forming the ink receiving layer of the recording medium of the present invention may contain benzethonium chloride as a quaternary ammonium compound which acts as a waterproofing agent. Benzethonium chloride is a compound represented by the following formula (III). As a commercial product, Hyamine 1622 (Sankyo Kasei Co., Ltd.)
Manufactured by Parke Davis Co.) and the like.

The main reason for containing benzethonium chloride in the coating liquid for forming the ink receiving layer of the recording medium of the present invention is that one has a quaternary ammonium group in the molecule of benzethonium chloride. The first is to reinforce the effect of suppressing the bleeding of the dye in the ink when the ink is recorded on the recording medium, and the second is to utilize the surface active effect. That is, benzethonium chloride lowers the surface energy of the coating liquid for forming the ink receiving layer,
This is because it is possible to facilitate the uniform application of the coating liquid to the surface of the non-woven fabric as the base material and allow the alumina hydrate in the coating liquid to sink between the fibers of the non-woven fabric.

The quaternary ammonium compounds exemplified above may be used alone or in combination of two or more kinds, but it is preferable to use benzethonium chloride for at least one kind, and further, it is preferable to use benzethonium chloride. The polyallylamine derivative represented by the formula (I) is used in combination, or benzethonium chloride and the fourth group represented by the general formula (II) are used.
It is preferable to use a primary ammonium salt type water-soluble resin in combination.

In these cases, the compounding ratio of the quaternary ammonium compound is such that when the benzethonium chloride and the polyallylamine derivative represented by the general formula (I) are used in combination, the coating liquid for forming the ink receiving layer is The content of benzethonium chloride is not particularly limited, but it is preferably 1 to 7% by weight in the total amount of the coating solution. When the content of benzethonium chloride is less than 1% by weight, the water resistance effect is not sufficiently exhibited, and when it exceeds 7% by weight, the water resistance may be deteriorated or the viscosity of the coating liquid may be increased. Further, when benzethonium chloride and the quaternary ammonium salt type water-soluble resin represented by the general formula (II) are used in combination, the content of benzethonium chloride in the coating liquid for forming the ink receiving layer is not particularly limited. However, it is preferably 0.5 in the total amount of the coating liquid.
~ 5% by weight. The content of benzethonium chloride is 0.
If it is less than 5% by weight, the water resistance effect will not be fully exhibited and
If it exceeds, the water resistance may deteriorate.

When the polyallylamine derivative represented by the general formula (I) is used as the quaternary ammonium compound, the content of the polyallylamine derivative in the coating liquid for forming the ink receiving layer is particularly limited. However, it is preferably 1 to 8% by weight in the total amount of the coating liquid. If the content of the polyallylamine derivative is less than 1% by weight, the water resistance effect is not sufficiently exhibited, and if it exceeds 8% by weight, the water resistance may be deteriorated or the viscosity of the coating liquid may be increased.

When a quaternary ammonium salt type water-soluble resin represented by the general formula (II) is used as the quaternary ammonium compound, the quaternary ammonium salt in the coating liquid for forming the ink receiving layer is used. The content of the ammonium salt type water-soluble resin is not particularly limited, but it is preferably 1 to 6% by weight based on the total amount of the coating liquid. When the content of the quaternary ammonium salt type water-soluble resin is less than 1% by weight, the water resistance effect is not sufficiently exhibited, and when it exceeds 6% by weight, the water resistance may be deteriorated or the viscosity of the coating liquid may be increased. .

Further, the compounding ratio with the alumina hydrate is
Although not particularly limited, it is preferably as follows. That is, when a polyallylamine derivative is used as the quaternary ammonium compound, it is preferably 3 to 11% by weight in the total amount of the coating liquid, and the quaternary ammonium compound is used as the quaternary ammonium compound.
When a graded ammonium salt type water-soluble resin is used, 0.5 to 11.0 wt% of the total amount of the coating liquid is preferable.

When the amount of alumina hydrate is less than the above range, the ink absorption of the coated recording medium is insufficient and the color development is insufficient, and when it exceeds the above range, the viscosity of the coating liquid increases, When a small amount is applied, it tends to be impossible to uniformly apply it on the nonwoven fabric which is the base material.

The image water resistance of a recording medium produced by these quaternary ammonium compounds is presumed to be exhibited by the action described below. That is, when water is dropped on the recording surface, the water droplets gradually penetrate into the recording medium or diffuse on the surface. The moving speed of the water at this time is determined by the type of the coating liquid on the recording medium, the type of the base material, the smoothness, etc., but it is about 1 mm / sec immediately after the dropping.
~ 30mm / sec, which is relatively fast, but eventually 1mm / s
The speed is slower than ec, and the moving time also requires a relatively long time until the drying of water is substantially started.
The longer the movement time of the water, the more the ink dye in the recording medium or the ink receiving layer is eluted by the osmotic pressure of the dripping water and appears as a bleed.

When a quaternary ammonium compound is added to the coating liquid for forming the ink receiving layer of the recording medium of the present invention, the addition of the quaternary ammonium compound into the coating liquid particularly in the above-mentioned combination makes it possible to add the dripping water. The reason why the water resistance is improved by is that the force of the alkyl group portion of the compound to be adsorbed to the recording medium or the pigment and the force of the ammonia portion being strongly linked with the dye molecules of the ink by the Coulomb force are superior to the osmotic pressure of the dripping water. This is because the bleeding of is no longer occurring. Further, since the effect of accelerating the moving speed of the dripping water also appears, it is presumed that this effect also contributes to the improvement of water resistance. Further, it goes without saying that the physical properties of the binder and the like described later also affect the water resistance performance. In the recording medium of the present invention, since the alumina hydrate easily sinks on the surface of the non-woven fabric, the natural texture of the non-woven fabric is maintained as it is. Does not happen.

However, when a pigment is mixed in addition to the alumina hydrate, or when surface smoothness and smooth writability are further required, a binder is added to the coating liquid for forming the ink receiving layer. May be added. Preferred binders include, for example, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic amide, vinyl acetate, oxidized starch, etherified starch, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, casein, gelatin, soybean protein, maleic anhydride resin, Conjugated diene copolymer latex such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, polymer of acrylic acid ester and methacrylic acid ester, or acrylic polymer latex such as copolymer, ethylene vinyl acetate Vinyl-based polymer latexes such as copolymers, or functional group-modified polymer latexes with functional group-containing monomers such as carboxyl groups of these various polymers, thermosetting synthetic resins such as melamine resins and urea resins of Sex binder, polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride - vinyl acetate copolymer, polyvinyl butyral, and synthetic resin binders such as alkyd resins.

These may be used alone or in admixture of two or more. Of these, water-soluble polymer binders are preferably used in the present invention.

Further, other white pigments may be used in combination depending on the ink jet suitability of the non-woven fabric as the base material, for example, color developability, resolution, water resistance and the like. As these white pigments, silica, zeolite, calcium carbonate, diatomaceous earth,
Kaolin clay, calcined clay, talc, aluminum hydroxide, colloidal alumina, alumina, barium sulfate,
Examples of pigments generally used for paper coating include titanium dioxide, zinc oxide, zinc carbonate, magnesium silicate, magnesium carbonate, and organic pigments (plastic pigments). Further, in order to add these pigments to the coating liquid for forming the ink receiving layer, it is necessary to uniformly disperse them in water. For this purpose, for example, sodium polyacrylate,
It is preferred to add conventional dispersants such as phosphates, surfactants and the like.

A surfactant may be added to the coating liquid for forming the ink receiving layer of the recording medium of the present invention. For example, anionic surfactants such as carboxylates, sulfonates, sulfates, phosphates, etc., aliphatic amine salts, aliphatic quaternary ammonium salts, aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts. Cationic surfactants such as salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, ether types such as polyoxyethylene polyoxypropylene block polymers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Nonionic surfactants such as ether ester type, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester type polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, and other nitrogen-containing surfactants, betaine Aminocarboxylates, amphoteric surfactants such as imidazoline derivatives.

In the coating liquid for forming the ink receiving layer of the recording medium of the present invention, other additives such as a pigment dispersant, a thickener, a fluidity improver, a defoaming agent, a defoaming agent, Release agent,
A foaming agent, a penetrating agent, a coloring pigment, a coloring dye, a fluorescent whitening agent, an ultraviolet absorber, an antioxidant, an antiseptic, an antifungal agent, a monomer, a polymer, an ink setting agent, a chelating agent, etc. may be appropriately added. it can.

The coating liquid for forming the ink receiving layer of the recording medium of the present invention comprises the above-mentioned constituents uniformly dispersed and dissolved in water by a usual method. As a dispersing method, it is preferable to use a dispersing machine such as a ball mill, an attritor, a sand mill, a homomixer, a Microfluidizer (manufactured by Microfluidex Co.), a nanomizer (manufactured by Nanomizer). The viscosity of the coating liquid can be changed depending on the coating method, coating device, coating amount, and support, but it is generally preferably 2000 cps or less. 200
When it is higher than 0 cps, it becomes difficult for the coating liquid to impregnate the non-woven fabric as the base material.

Next, a method for manufacturing the ink jet recording medium of the present invention will be described. As the method for producing an inkjet recording medium of the present invention, at least one or more ink receiving layers are applied and / or applied to the non-woven fabric as a substrate by using the above-mentioned coating liquid or a size press device. Impregnate. The coating method may be either an on-machine coater or an off-machine coater, a conventionally known roll coater, air knife coater, die coater, blade coater, gate roll coater, bar coater, rod coater, roll coater, gravure coater, A curtain coater etc. can be used. After coating, the coating liquid is dried by blowing hot air. The temperature and the air flow of the hot air vary depending on the type of the nonwoven fabric as the base material used, the composition of the coating liquid, and the like, but are preferably 70 to 160 ° C. Generally 70
If the temperature is lower than ℃, it takes a long time to dry, and if the temperature is higher than 160 ℃, the base material may be modified in the non-woven fabric or the coating liquid.

After coating, calender treatment such as machine calender, super calender, soft calender and the like may be performed to finish. In the present invention, when the coating liquid is applied on one side, a back coat layer may be provided on the surface of the substrate opposite to the ink receiving layer. The composition of the back coat layer may be the same as or different from the composition of the ink receiving layer, and its coating amount, coating method and the like are not particularly limited. If necessary, these recording media may be provided with an adhesive layer, an adsorption layer, a peeling layer, a foaming layer and the like.

The ink used as a recording agent in the recording medium of the present invention is a recording agent composed of the following coloring agent, liquid medium and other additives. Examples of the colorant include direct dyes, acid dyes, basic dyes, reactive dyes, and water-soluble dyes such as food colorings. Water and various water-soluble organic solvents can be used as the liquid medium.

The recording medium of the present invention is particularly suitable as an inkjet recording medium, but can be used not only in the inkjet recording method but also in any recording method using a liquid ink during recording. it can.
As such a recording method, for example, a heat-meltable substance,
A thermal transfer recording method in which a medium coated with a heat-melting ink mainly composed of dyes and pigments on a resin film, high-density paper, synthetic paper, or another thin substrate is heated from the back side and the ink is used as a solvent for transfer. , A solid ink jet recording method in which a heat-meltable ink is melted by heating to form fine droplets and flying to record, an ink jet recording method using an ink in which an oil-soluble dye is dissolved in a solvent, a photopolymerizable monomer and a colorless or colored ink A recording method using a pressure-sensitive type donor sheet using microcapsules containing dyes and pigments may be used. The common feature of these printing methods is that the ink is in a liquid state during printing.

The liquid ink permeates or diffuses in the depth direction or the horizontal direction of the ink receiving layer of the recording medium before being cured, solidified, or fixed. The recording media for these various recording systems require absorptivity according to each system, and there is no problem even if the recording medium of the present invention is used as these recording media. Further, the ink jet recording medium of the present invention may be used as a recording medium for heating and fixing an electrophotographic recording toner widely used in copiers and printers.

[0042]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The BET specific surface area of the alumina hydrate, the pore size distribution of the alumina hydrate and the alumina hydrate in the ink receiving layer, the pore volume, the isothermal nitrogen adsorption / desorption curve, etc. are simultaneously determined by the nitrogen adsorption / desorption method. Can be here
Alumina hydrate or a recording medium having a receptive layer formed on a PET film was sufficiently heated and deaerated, and then measured using Autosoap 1 manufactured by Cantachrome. The BET specific surface area was calculated by the method described in Brunauer et al. (J.
Am.Chem.Soc., 60, 309, 1938). In addition, the method described in Barrett et al. Was used to calculate the pore diameter and pore volume (JA
m.Chem.Soc., 73, 373, 1951).

Base material A pulp and acrylic fibers are accumulated, and the basis weight is 78 g.
/ M ² non-woven fabric. Base B pulp and polyester fibers are accumulated, and the basis weight is 5
Non-woven fabric of 0 g / m ² .

Preparation of Coating Liquid Coating Liquid A Alumina hydrate (Product described in Example A of JP-A-7-89221; BET specific surface area of 76 m ² / g; BET pore volume of 0.
(57 ml / g) 60 g was added to ion-exchanged water 240 g, stirred with a stirrer for 30 minutes, and then dispersed with a homomixer at 8000 rpm for 30 minutes to obtain an alumina slurry. 90 g of this slurry was weighed, and 120 g of polyallylamine derivative (PAA-10C manufactured by Nitto Boseki Co., Ltd .; active ingredient concentration 10%), benzethonium chloride (Hiamine 1622 manufactured by Sankyo Kasei Co., Ltd .; active ingredient concentration 100)
%) 12 g and ion-exchanged water 78 g were added, and the mixture was stirred with a three-one motor for 30 minutes. The viscosity of the prepared coating liquid is 670 cps (B type rotational viscometer HM-3; 30 rpm;
25 ° C).

Coating liquid B 90 g of the alumina slurry prepared in the coating liquid A was weighed out to obtain a polyallylamine derivative (P manufactured by Nitto Boseki Co., Ltd.).
AA-15B; active ingredient concentration 15%) 80 g, benzethonium chloride (manufactured by Sankyo Kasei Co., Ltd., Hyamine 162)
2; active ingredient concentration 100%) 9 g, ion-exchanged water 121
g was added and stirred for 30 minutes with a three-one motor.
The viscosity of the prepared coating liquid was 1450 cps (B type rotational viscometer HM-3; 30 rpm; 25 ° C.).

Coating liquid C 45 g of the alumina slurry prepared in the coating liquid A was weighed out, and a quaternary ammonium salt type water-soluble resin (Wastex H-90 manufactured by Nagase Kasei Co., Ltd .; active ingredient concentration 1)
20%, benzethonium chloride (Hyamine 1622 manufactured by Sankyo Kasei Co., Ltd .; active ingredient concentration 100%)
6 g, 1.5 g of a silicon-based defoaming agent (FS Antifoam 91 manufactured by Dow Corning; active ingredient concentration of 16%), and 229 g of ion-exchanged water were added, and 30 were added with a three-one motor.
Stirred for minutes. The viscosity of the prepared coating liquid is 330 cps
(B type rotational viscometer HM-2; 30 rpm; 25 ° C.).

Coating liquid D Alumina hydrate (BET specific surface area 68.5 m ² / g; B
60 g of ET pore volume 0.75 ml / g) was added to 240 g of ion-exchanged water and stirred with a stirrer for 30 minutes,
A homomixer dispersed at 8000 rpm for 30 minutes to obtain an alumina slurry. Weigh 90g of this slurry,
A coating liquid was prepared in the same manner as the coating liquid A. The viscosity of the prepared coating liquid is 790 cps (B type rotational viscometer HM-2; 3
0 rpm; 25 ° C).

Coating liquid E Alumina hydrate (BET specific surface area 284 m ² / g; BE
T pore volume 0.24 ml / g) 60 g of ion-exchanged water 2
It was put into 40 g, stirred for 30 minutes with a stirrer, and then dispersed with a homomixer at 8000 rpm for 30 minutes to obtain an alumina slurry. 90 g of this slurry was weighed out and a coating liquid was prepared in the same manner as the coating liquid A. The viscosity of the prepared coating liquid is 370 cps (B type rotational viscometer HM-2; 30
rpm; 25 ° C).

Coating liquid F Alumina hydrate (BET specific surface area 184 m ² / g; BE
T pore volume 0.87 ml / g) 60 g of ion-exchanged water 2
It was put into 40 g, stirred for 30 minutes with a stirrer, and then dispersed with a homomixer at 8000 rpm for 30 minutes to obtain an alumina slurry. 90 g of this slurry was weighed out and a coating liquid was prepared in the same manner as the coating liquid A. The viscosity of the prepared coating liquid is 1100 cps (B type rotational viscometer HM-2; 3
0 rpm; 25 ° C).

Coating liquid G for comparative example G Alumina hydrate was added to BET specific surface area 328 m ² / g BE
A coating liquid was prepared in the same manner as the coating liquid A using a T pore volume of 0.24 ml / g. The viscosity of the prepared coating liquid is 1780 cps (B type rotational viscometer HM-3 30 rp
m 25 ° C).

Coating Liquid I for Comparative Example I Alumina hydrate with BET specific surface area of 123 m ² / g; BE
A coating liquid was prepared in the same manner as the coating liquid A using T pore volume of 0.18 ml / g. The viscosity of the prepared coating liquid is 1420 cps (B type rotational viscometer HM-3; 30 rp
m; 25 ° C).

Coating liquid for comparative example J BET specific surface area of 169 m ² / g;
A coating liquid was prepared in the same manner as the coating liquid A using a T pore volume of 0.95 ml / g. The viscosity of the prepared coating liquid is 1700 cps (B type rotational viscometer HM-3; 30 rp
m; 25 ° C).

Coating liquid K for comparative example The same as coating liquid A was prepared by using amorphous silica (BET specific surface area 55 m ² / g; BET pore volume 0.08 ml / g) instead of alumina hydrate. To prepare a coating liquid. The viscosity of the prepared coating liquid is 1300 cps (B type rotational viscometer HM-
3; 30 rpm; 25 ° C).

Coating Liquid L for Comparative Example A coating liquid was prepared in the same manner as the coating liquid A without adding the polyallylamine derivative in the coating liquid A. The viscosity of the prepared coating liquid is 160 cps (B type rotational viscometer HM-3; 30
rpm; 25 ° C).

Coating Liquid M for Comparative Example A coating liquid was prepared in the same manner as the coating liquid A without adding benzethonium chloride in the coating liquid A. The viscosity of the prepared coating liquid is 1200 cps (B type rotational viscometer HM-3; 30r
pm; 25 ° C).

Method for producing recording medium The above coating solutions were coated on one surface of the above-mentioned support in the combinations shown in Tables 1 and 2 to produce recording media of the present invention and comparative examples. Examples 13 and 14 were coated on both sides. Coating method: Roll coater Coating amount: As shown in Table 1 Drying temperature: 130 ° C. hot air Drying time: 3 minutes The produced recording medium was evaluated as follows. The evaluation results are shown in Tables 1 and 2.

Recording Evaluation Recording for evaluation was performed using an inkjet printer (BJC-600S, BJ Color Printer, manufactured by Canon Inc.). Image Density The optical densities of solid printed portions of yellow, magenta, cyan and black were measured with a Macbeth reflection densitometer RD-1255. Print a straight line with a width of 1 dot parallel to the scanning direction of the print quality head.
Visual evaluation from a distance of 25 cm was performed.
What was visible as a clear straight line was designated as A, and as it became more unclear, it was designated as B and C.

Water-Resistant Immersion Water-Resistant : The solid printed portion was immersed in tap water for 3 seconds, then pulled up and naturally dried. It was visually confirmed whether ink flow occurred after drying. The ink in which no ink flow was observed was designated as A, and B and C were designated as they flowed. Dripping water resistance : Nine lines were printed on a 2 cm square frame at intervals of 2 mm in a checkered pattern with a printer, and one drop of tap water was dropped onto the center of the frame. After air-drying, it was visually confirmed whether the checkered line was distorted and bleeding occurred. A that does not show any distortion or blurring is
As they flowed, they were designated as B and C.

[0059]

[Table 1]

[0060]

[Table 2]

From the above results, a recording medium obtained by coating and / or impregnating a non-woven fabric with a coating liquid containing an alumina hydrate and a specific quaternary ammonium compound is particularly excellent in ink jet recording characteristics and water resistance. You can see that

[0062]

The following effects are brought about by the recording medium of the present invention. (1) A non-woven fabric capable of forming an image with high color development and high water resistance suitable for inkjet recording was obtained. (2) By impregnating the fibers of the non-woven fabric with alumina hydrate, which has a high absorbability for the ink-jet ink, an ink jet recording medium having a non-woven fabric texture and a soft feeling was obtained. (3) It has become possible to obtain a small number of non-woven fabric prints at low cost, which was difficult with conventional printing.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a recording medium of the present invention.

FIG. 2 is a schematic cross-sectional view showing another example of the recording medium of the present invention.

FIG. 3 is a schematic cross-sectional view showing another example of the recording medium of the present invention.

[Explanation of symbols]

 1: Ink receiving layer 1a: Ink receiving layer 1b: Ink receiving layer 1c: Ink receiving layer 2: Base material (nonwoven fabric)

Claims (12)

[Claims] 1. A recording medium, wherein an ink receiving layer containing at least an alumina hydrate is formed on the surface and inside of a non-woven fabric constituted by accumulating a large number of continuous filaments. 2. The BET specific surface area of hydrated alumina is 60.
The recording medium according to claim 1, wherein the recording medium has a density of 300 m ² / g. 3. The BET pore volume of alumina hydrate is 0.
The recording medium according to claim 1, which is 2 to 0.9 ml / g. 4. The recording medium according to claim 1, wherein the alumina hydrate is an amorphous amorphous alumina hydrate. 5. The recording medium according to claim 1, wherein the ink receiving layer further contains one or more quaternary ammonium salt compounds. 6. The recording medium according to claim 5, wherein at least one of the quaternary ammonium salt compounds is a polyallylamine derivative having a structural unit represented by the following general formula (I) as a constitutional unit. (In the above formula, x ⁻ is Br ⁻ , Cr ⁻ , I ⁻ , HOSO ₃ ⁻ , CH.
₃ OSO ₃ ⁻ or C ₂ H ₅ OSO ₃ ⁻ , and n is 5 to 1
Represents a number of 10,000. ) 7. The quaternary ammonium salt-type water-soluble resin, wherein at least one of the quaternary ammonium salt compounds is a quaternary ammonium salt type water-soluble resin having a structural unit represented by the following general formula (II) as a constitutional unit. The recording medium described. 8. The recording medium according to claim 5, wherein the quaternary ammonium salt compound contains benzethonium chloride. 9. A polyallylamine derivative having a structural unit represented by the general formula (I) as a constitutional unit in an amount of at least 3 to 11% by weight of an alumina hydrate on the surface and inside of a nonwoven fabric at an effective component concentration of 1 to 8% by weight. % And benzethonium chloride 1-7
A method for producing a recording medium, which comprises applying and / or impregnating a coating liquid comprising an aqueous dispersion containing 10% by weight to form an ink receiving layer. 10. A water-soluble quaternary ammonium salt of the structural formula represented by the general formula (II), wherein 0.5 to 11.0% by weight of an alumina hydrate is contained on the surface and the inside of the nonwoven fabric at least at an active ingredient concentration. A recording characterized in that an ink receiving layer is formed by coating and / or impregnating a coating liquid comprising an aqueous dispersion containing 1 to 6% by weight of resin and 0.5 to 5.0% by weight of benzethonium chloride. Medium manufacturing method. 11. An inkjet recording medium comprising the recording medium according to any one of claims 1 to 8. 12. An ink jet recorded matter having an image formed by an ink jet method on at least one surface of the ink jet recording medium according to claim 11.