JP2001080223A - Recording medium and recording method - Google Patents

Abstract

(57) [Problem] To be used in a full-color image recording method in which a recording liquid is discharged as droplets from a recording unit by means such as selective heating and is transferred to an opposing recording paper.
Providing recording paper with excellent density gradation and storage stability. SOLUTION: A recording liquid containing a recording material and a medium for dissolving or dispersing the recording material is supplied to a recording liquid flying section,
A recording medium used in a recording method in which the recording liquid is heated to be vaporized, sublimated, or converted into droplets, and these are transferred and adhered to a recording medium disposed opposite to the recording liquid flying section (recording head). A recording medium comprising a support and a fixing layer containing a montmorillonite group mineral as a main component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for heating a recording liquid from a recording section by means of selective heating or the like, causing the recording liquid to be vaporized, sublimated, or ejected in the form of fine droplets, and transferred to the opposing recording paper. The present invention relates to a recording paper used in a full-color image recording method. In particular, with respect to a recording medium used in a recording apparatus of a new recording method which has solved the disadvantages of both the thermal transfer method and the ink jet method, the recording density, image quality,
To provide a recording image having excellent storage stability.

[0002]

2. Description of the Related Art In recent years, with the progress of colorization of image recording of video cameras, televisions, computer graphics, and the like, the need for colorization of hard copies has rapidly increased. In response, various types of color printers have been developed and are being deployed in various fields. Among these recording methods, methods for easily outputting high-quality images with a simple apparatus can be broadly classified into a dye diffusion thermal transfer system (sublimation thermal transfer system) and an ink jet system. Among these recording methods, the dye diffusion thermal transfer method uses an ink sheet in which an ink layer in which a high-concentration transfer dye is dispersed in an appropriate binder resin is applied, and a dyeing resin that receives the transferred dye. The processed recording medium is brought into close contact with a fixed pressure, and heat is applied from the thermal recording head located on the ink sheet in accordance with the image information, and the recording medium is heated from the ink sheet in accordance with the amount of heat applied. The transfer dye is thermally transferred to the dye receiving layer.

The so-called thermal transfer method is characterized in that the above operation is repeated for each of the image signals separated into the three subtractive primary colors, ie, yellow, magenta and cyan, thereby obtaining a full-color image having continuous gradation. Has attracted attention as an excellent technique for obtaining a high-quality image comparable to silver halide color photography, which is easy to miniaturize, easy to maintain, has immediacy. However, this method has a major drawback in that a large amount of waste is generated due to disposable ink sheets and high running costs are involved.

On the other hand, in the ink jet system, small droplets of a recording liquid are provided on a recording head by a method such as an electrostatic suction system, a continuous vibration generation system (piezo system), or a thermal (bubble jet) system in accordance with image information. The recording is performed by causing the nozzles to fly from the nozzles that have been made to adhere to the recording medium.
In this case, the recording liquid comprises a dye solution in which a dye is dissolved in a solvent (or a dispersion in which a pigment is dispersed in a solvent). The recording liquid is ejected as fine droplets from the nozzles by a force such as vibration, flies and moves in the gap between the nozzle and the recording medium, and is continuously supplied to the recording medium to form an image. This operation is repeated at each nozzle by using, for example, three nozzles with respect to an image signal decomposed into four colors obtained by adding black to the three primary colors of subtractive color mixing, that is, yellow, magenta, cyan and possibly the three primary colors. And a full-color image can be recorded.

[0005] Unlike the thermal transfer method using an ink sheet or the like, the ink jet method hardly generates waste. However, in the ink jet method, since the size of the droplet is determined by the size of the opening at the tip of the nozzle, it is in principle difficult to adjust the density gradation in the pixel. For this reason, the expression of shading depends on the area gradation (the size of the transfer area), and the resolution of the image is reduced. For this reason,
It is difficult to reproduce a high-quality image comparable to a silver halide photograph, as obtained by a dye diffusion thermal transfer system. Plain paper can also be used as the recording medium of the ink jet system. However, in order to obtain higher-density and higher-quality recording, a coating mainly composed of a pigment such as silica having high ink absorption and an adhesive is used. Dedicated paper provided with a working layer is used.

[0006] The above-mentioned disadvantages of both the thermal transfer system and the ink jet system are solved, high image quality and immediacy are provided, the apparatus can be reduced in size and weight, and waste such as used transfer film is generated. A recording method described in Japanese Patent Application Laid-Open No. 8-169171 or the like has been proposed as a recording method capable of recording on plain paper without using it, and performing with low power consumption and low running cost.

[0007]

According to this method, a porous structure, for example, a large number of fine columnar bodies (for example, each having a size and an interval of 0.1 mm) is provided in a recording liquid flying section (for example, a recording liquid heating section) of a recording head. A columnar body having a size of about 10 to 10 μm is used.
15 μm), and supplies a recording liquid containing a recording material and a substance (also referred to as a medium or a carrier) which dissolves or disperses the recording material and which expands in volume by heating, for example, to a recording liquid flying section; This is a recording method in which the recording liquid is extruded by means such as pressurization or thermal expansion to form liquid droplets, and the liquid droplets are transferred to a recording medium arranged to face the recording head. According to this recording method, the surface area is increased by providing the above-described porous structure in the recording liquid flying section, and the recording liquid can be constantly supplied to the recording liquid flying section by capillary action and held there. In this state, a part of the recording liquid is selectively applied by a heating means, which is a means for changing the state of the recording liquid, for example, according to the recording information by means of a heating means. The image is transferred to the recording medium by an amount corresponding to the recording information corresponding to the desired image, and is transferred onto the recording medium.

In this case, as compared with the known ink jet system, the fine pores of the porous structure described above correspond to those of the conventional ink jet system nozzle having a hole diameter of several tens μm. A large number of small-sized dropletized recording liquids can be formed, and the transfer amount of the recording liquid (that is, the amount of flying recording liquid) can be freely adjusted according to applied energy such as heating energy corresponding to the recording information to the recording liquid flying section. Control, so that density gradation is possible,
It is possible to obtain a recording having an image quality equal to or higher than that of the silver halide image. According to this method, it is possible to record on plain paper.However, when recording on ordinary high-quality paper or medium-quality paper, the fixability of the dye in the recording liquid is insufficient, so , Image quality and storability are insufficient. SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and to provide a recording medium for use in a new recording method which eliminates the disadvantages of conventional recording methods such as a thermal transfer recording method and an ink jet recording method. Another object of the present invention is to provide a recording medium having excellent recording density, image quality, density gradation, and storage stability.

[0009]

According to the present invention, a recording liquid containing a recording material and a substance for dissolving or dispersing the recording material is supplied to a recording liquid flying section, and the recording liquid is formed into droplets. A recording method used for a recording method in which droplets are transferred to a recording medium disposed opposite to a recording liquid flying section (recording head) (particularly, a new recording method in which the recording liquid flying section of the recording head is formed of a porous structure). It has been found that, by using a recording medium in which a fixing layer containing a montmorillonite group mineral is provided on a support, recording excellent in recording density, image quality, density gradation, and storability can be obtained.

[0010] The recording medium of the present invention comprises: a recording liquid containing a recording material and a medium for dissolving or dispersing the recording material;
The recording liquid is supplied to a recording liquid flying means composed of a porous structure, and the recording liquid is heated to be vaporized, sublimated, or converted into fine droplets, and the recording medium is disposed to face the recording liquid flying means. A recording medium used in a recording method for transferring and adhering to a recording medium, comprising: a support; and a fixing layer provided on the support and containing a montmorillonite group mineral.

In the recording medium of the present invention, the montmorillonite group mineral is represented by the following composition formula (1): (X, Y) _2-3 Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (W
_1/3 ) (where, in the formula (1), X is Al, Fe (III), Mn
(III) or Co (III), where Y is Mg, Fe (I
I), represents Ni, Zn or Li, where Z is Si or Al
W represents K, Na or Ca, H ₂ O represents interlayer water, and m represents 0 or an integer of 1 or more. ) Are preferred. In the recording medium of the present invention, a gloss layer containing a thermoplastic polymer substance and a fine pigment may be further provided on the fixing layer. In the recording medium of the present invention, the thermoplastic polymer substance of the gloss layer contains at least one selected from a polyester resin and an acrylic resin, and the fine pigment of the gloss layer has an average of 1.0 μm or less. It preferably has a particle size. In the recording medium of the present invention, the fine pigment of the gloss layer is aluminosilicate, amorphous silica, colloidal silica, calcined kaolin,
It is preferable to include at least one selected from diatomaceous earth and urea-formaldehyde resin particles. In the recording medium of the present invention, the fixing layer preferably contains a binder resin and a porous pigment together with the montmorillonite group mineral. In the recording medium of the present invention, the fixing layer may further contain a surfactant.
The recording method of the present invention uses the recording medium of the present invention,
A recording liquid containing a recording material and a medium for dissolving or dispersing the recording material is supplied to a recording liquid flying means comprising a porous structure, and the recording liquid is vaporized by heating,
It is characterized by sublimation or formation of fine droplets, which are transferred to and adhered to a recording medium arranged opposite to the recording liquid flying means.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the support is not particularly limited, and various papers, synthetic papers, plastic films, metal foils and the like are appropriately used. Among them, from the viewpoints of cost, ease of handling, and easy disposal,
Paper is preferred. Specific examples include medium quality paper, high quality paper, coated paper, art paper, cast coated paper, and laminated paper. The support may be an opaque type or a transparent type. An opaque support is used for observation with reflected light, and a transparent support is used for observation with transmitted light (for example, OHP). In an embodiment using an opaque support, the opacity is preferably 80% or more, more preferably 90% or more. When a transparent support is used, the fixing layer and the gloss layer can be designed to be transparent to provide a transparent recording medium, which is suitable for use in OHP and the like.
In this embodiment, the haze of the transparent support is preferably 10% or less. In the recording medium of the dye thermal transfer recording method, it is necessary to use a support having a high heat insulating property or a cushioning property or to provide an undercoat layer having a high heat insulating property or a cushioning property in order to increase the recording density. However, such consideration is not particularly required as long as the present recording method is used.

Next, the ink fixing layer of the present invention will be described. The ink fixing layer is a layer containing a montmorillonite group mineral as a main component. In the recording method of the present invention, the recording liquid contains a substance (carrier) that dissolves or disperses the recording material such as a dye and converts the recording material into a droplet by heating, for example, in addition to the recording material such as a dye. It is necessary to absorb and fix the containing recording liquid. In addition, absorption
Other inorganic or organic pigments can be blended to improve fixing ability. By mixing an inorganic or organic pigment, the fixing layer can be made porous. In addition, by adding a surfactant, preferably a nonionic surfactant, the recording liquid can be quickly absorbed and retained, preventing bleeding of an image and obtaining a recording medium having excellent resolution. Can be It is preferable that the inorganic or organic pigment itself is porous, but even if the inorganic or organic pigment is not porous, by adjusting the mixing ratio of the binder resin and the fine particles and the montmorillonite group mineral, the inorganic or organic pigment can be used. Voids can be formed between the pigments. The porosity can be confirmed by observing the fixing layer with an electron microscope (about 1,000 to 10,000 times). More preferably, the porous pigment has an oil absorption of 50 ml / 100 g or more.

The montmorillonite group mineral is an intercalation compound that receives and holds the recording solution by an intercalation reaction. An intercalation reaction occurs between a recording material (dye), which is a recording liquid component, and a medium (carrier) for dissolving or dispersing the recording material, and is fixed. The montmorillonite group mineral used in the present invention is typically
It has an octahedral smectite structure and can be represented by the following formula (1). (X, Y) _2-3 Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (W _1/3 ) (1) (where X is Al, Fe (III), Mn (III) or C
o (III), Y is Mg, Fe (II), Ni, Zn
Or Li, Z is Si or Al, W is K,
Na or Ca, H ₂ O is interlayer water, and m
Represents an integer. Specifically, montmorillonite, magnesia montmorillonite, iron montmorillonite, iron magnesia montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontronite, saponite, aluminum Natural products and synthetic products such as nian saponite, hectorite and sauconite can be exemplified. In addition, those in which the OH group in the above formula (1) is substituted with fluorine can also be used. Further, those obtained by subjecting the above-mentioned montmorillonite group mineral to inorganic or organic treatment can also be used. By such a treatment, for example, the affinity with various solvents can be improved.

The fixing layer of the recording medium of the dye thermal transfer recording system is formed by heat blocking (sticking) of the color material transfer film.
In order to prevent, it is necessary to select a resin in consideration of the releasability, or it is necessary to mix a material that imparts releasability,
This recording method does not particularly require such consideration. Examples of the binder resin contained in the fixing layer include polyester resin, urethane resin, vinyl acetate resin, acrylic resin, polyvinyl chloride resin, polycarbonate resin, acetate resin, and polyvinylpyrrolidone. Among them, a saturated polyester resin, a urethane resin, and a copolymer resin of vinyl acetate and acryl, ethylene, and the like are more preferably used from the viewpoint of print density and storage stability. The glass transition point of the binder resin is not particularly limited, but is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, in order to effectively adsorb the dye or the like of the recording liquid. If the glass transition point is too high, the recording density tends to decrease. This is presumably because the film-forming properties of the resin deteriorated, the surface became porous, and the recording liquid penetrated into the recording layer and did not remain on the surface. However, if the glass transition point is too low, the fixing layer in the fixing layer forming step becomes sticky or causes a blocking phenomenon, which is an obstacle in production, or the storage stability of the recorded image is poor, and the image tends to blur. Therefore, -1
Those having a temperature of 0 ° C. or higher are more preferable.

The surfactant used in the present invention is preferably a nonionic surfactant such as polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene fatty acid esters. It is preferable to include at least one type. The nonionic surfactant reacts with the ionicity of the colorant in the ink, and is particularly preferable because there is no fear of aggregation. In the recording material of the present invention, by forming a fixing layer containing a surfactant on a support, the ink absorbing speed when an ink containing a dye comes into contact with the fixing layer can be increased, and the ink described above can be used. Are firmly fixed in the fixing layer by an intercalation reaction.

Examples of the inorganic or organic pigment contained in the fixing layer include amorphous silica, alumina, mica, zeolite, colloidal silica (dispersion of primary particles), kaolin, clay, calcined clay, zinc oxide, Inorganic pigments such as tin oxide, magnesium sulfate, aluminum oxide, aluminum hydroxide, calcium carbonate, satin white, aluminum silicate, smectite, magnesium silicate, magnesium carbonate, magnesium oxide, diatomaceous earth, styrene plastic pigment, acrylic plastic pigment, urea Organic pigments such as resin-based plastic pigments, benzoguanamine-based plastic pigments, and acrylonitrile-based plastic pigments, and various other pigments known and used in the general coated paper field are appropriately used. The particle size of the inorganic or organic pigment is not particularly limited, but may be 0.1 to 0.1.
It is preferably in the range of ２０20 μm. When the thickness is less than 0.1 μm, it becomes difficult for the fixing layer to form a porosity enough to quickly absorb the recording liquid, and bleeding may occur and image quality may be reduced. In some cases, the adhesion of the recording liquid becomes uneven, and the image quality and the recording density may decrease. Further, the pigment itself is preferably porous, and the oil absorption is preferably 50 ml / 100 g or more. Since the pigment itself is porous and has an ink absorbing ability, the amount of the pigment added can be easily adjusted, and the quality such as glossiness can be further improved. Oil absorption 50ml / 1
If it is less than 00 g, the amount of addition cannot be reduced. The oil absorption of the pigment to be added is more preferably 80 ml / 100 g.
That is all. There is no upper limit for oil absorption, but 400ml / 100g
Up to a degree are available. The inorganic or organic pigment is used in an amount of 5 to 100 parts by weight of the montmorillonite group mineral.
It is preferable to add about 200 parts by weight.

Among the above inorganic or organic pigments, mica,
Aluminosilicates such as zeolites have excellent ink-absorbing ability and have a great effect on storage stability (prevention of browning), and thus are preferably used as at least a part of inorganic or organic pigments. Among the aluminosilicates, crystalline aluminosilicates, ie zeolites, are particularly preferred. Zeolites include natural zeolites and synthetic zeolites, and more than 100 are known. As a typical one,
Examples of natural zeolites include japsite, erionite, mordenite, clinobutyrolite, and the like.
Examples of the synthetic zeolite include A type, X type, Y type, and T type. Among them, synthetic zeolite is preferably used because it has high purity and stable composition and uniform particle size.

In the present invention, the weight ratio of the binder resin such as a thermoplastic polymer substance used for the fixing layer to the pigment solids such as the montmorillonite group minerals and inorganic or organic pigments is appropriately set according to these types. Although it is not particularly limited, it is preferably adjusted in the range of 95/5 to 5/95, more preferably 90/10 to 10/90. If the blending amount of the binder resin is too large, the gap of the fixing amount becomes too small, and the bleeding and the ink absorbability are deteriorated. On the other hand, if the amount of the thermoplastic polymer compound is too small, the fixing layer is cracked, the strength is inferior, the state becomes unusable, the recording density is reduced, and the storability of the recorded image is reduced. There is a risk.

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 appropriately added. The coating amount of the fixing layer is not particularly limited, 1~100g / m ^2, preferably preferably adjusted with 5 to 60 g / m ^2. 1g
/ M ^2, it is difficult to obtain the desired effect, and 100 g / m ²
It exceeds m ² when effect tends to be saturated. The layer of the present invention may be a single layer or a multilayer. Corona treatment and various kinds of anchor coat treatments on the substrate can be performed for the purpose of increasing the adhesion. The fixing layer can be formed by a single layer or a laminate of two or more layers.

In order to provide glossiness and give the same feeling as silver halide photography, it is preferable to provide a glossy layer on the fixing layer. The gloss layer contains a resin. As resin,
Examples of the binder for the fixing layer include the resins exemplified above, and particularly preferred are polyester resins and acrylic resins. The gloss layer can contain a pigment, but a fine pigment is used in order not to impair the gloss. Preferably the average particle size is 1 μm or less, more preferably 0.6 μm
Hereinafter, a fine pigment having a particle size of 0.3 μm or less, most preferably 0.1 μm or less is more preferable.

The polyester resin for the binder is not particularly limited, but preferably has a recording material fixing property. For example, a linear polyester resin or an aromatic polyester resin is preferably used. The acrylic resin is not particularly limited as in the case of the polyester resin. However, as a resin used for the glossy layer, a resin that does not swell with the medium contained in the recording liquid or does not impair the fixability of the recording material is preferable as a feature of the present recording method. The degree of swelling is related to the glass transition point. When it is not necessary to fix the recording material on the gloss layer as in the fixing layer, the glass transition point of the polyester resin and / or acrylic resin used for the gloss layer is not particularly limited. However, especially when the recording density is high, it is necessary to fix the recording material on the glossy layer, and the glass transition point of the resin is 150 ° C. like the fixing layer.
Or less, more preferably 100 ° C. or less. In particular, in the case of a glossy layer, if the glass transition point is too high, it becomes difficult to develop glossiness. Therefore, a resin having a temperature of 80 ° C. or lower is more preferably used. The glass transition point of the resin used is appropriately selected depending on the pigment ratio and the like, but is preferably 0 ° C. or higher. When the glass transition point is lower than 0 ° C., the glossy layer which is the surface layer is sticky, so-called blocking tends to occur, and it may be difficult to handle when carrying by hand.

As the pigment used in the gloss layer, a fine pigment having an average particle diameter of 1 μm or less is preferably used.
If the average particle size exceeds 1 μm, the glossiness of the glossy layer is reduced, so that the desired texture similar to that of a silver salt photograph cannot be obtained. Further, as the fine pigment, for example, amorphous silica, which is porous in order to have a recording liquid absorbing property,
For example, calcined kaolin, colloidal silica, urea, formalin resin, etc.
Aluminosilicate, diatomaceous earth and the like having a function of fixing the recording material to the pigment are preferably used. The fine pigment used for these glossy layers has a function of giving instant absorption of the recording liquid, and the mixing ratio of this pigment to the above resins is 2%.
0:80 to 10:90 is preferable, and 4 is more preferable.
It is about 0:60 to 85:15. When the pigment ratio is high, the film strength of the glossy layer is reduced, which may cause damage to an image and a recording medium. On the other hand, if the pigment ratio is too low, the absorbency of the recording liquid is reduced, which may cause stains on the image such as tailing by a recording head, a guide roll, or the like, and may cause contamination on the recording medium due to stickiness. The coating amount of the gloss layer is
Although it depends on the composition and the component ratio of the contained resin and pigment, it is preferable to use 0.1% in order to give the recording liquid absorptivity and gloss.
5 to 10 g / m ² is preferable, and ² to 7 g is more preferable.
/ M ² . If it is less than 0.5 g / m ^2, it is difficult to develop glossiness, while if it exceeds 10 g / m ² , the strength of the glossy layer may be extremely reduced. The 75 degree glossiness is preferably 20% or more, more preferably 40% or more, and further preferably 60% or more.

Coating devices for obtaining a fixing layer or a gloss layer include blade coaters, air knife coaters, roll coaters, bar coaters, gravure coaters, rod blade coaters, die coaters, lip coaters, and the like.
Various known materials such as a curtain coater can be used. In order to improve the gloss, the film may be smoothed by a calender, and may be provided by a cast coating method or a film casting method.

The recording liquid used in the recording method of the present invention comprises, as essential components, a recording material (dye) for forming an image and a medium (carrier) for dissolving or dispersing the recording material. Accordingly, the composition is adjusted by adding various dispersants, surfactants, viscosity modifiers, specific resistance regulators, pH regulators, fungicides, and the like. An undercoat layer containing a resin is provided on the support,
Effects such as improving the adhesion of the ink fixing layer can also be obtained.

As the recording material, a dye selected from the group consisting of disperse dyes, oil-soluble dyes, basic dyes, acid dyes, cationic dyes and direct dyes, and coloring pigments such as phthalocyanine and carbon black can be used. Among these, disperse dyes such as anthraquinone-based, indoaniline-based, styryl-based, azo-based and quinophthalone-based dyes have coloring properties,
It is preferably used in terms of fixability, storage stability and the like. The disperse dye is dissolved at a high concentration in a medium having a high boiling point, and is excellent in print density.
These dyes or pigments may be used as a mixture of two or more in order to adjust hue and sensitivity.

As the medium (carrier), the above dye or pigment is dissolved or dispersed and has a melting point of 150 ° C. or less.
It is preferable to use a substance whose boiling point at 1 atm is 150 to 350 ° C. If the boiling point of the carrier is lower than 150 ° C. like water, it is quickly evaporated and lost in the recording liquid flying portion of the recording head, so that only the recording material easily remains in the recording liquid, and the boiling point is 350 ° C. Is exceeded, it becomes difficult to efficiently transfer the carrier into droplets even when heating or the like for recording is performed. The carrier is preferably a plasticizer that is colorless and transparent and has the ability to dissolve or disperse the dye or pigment described above. Further, it is preferable that thermal decomposition does not occur below the boiling point. Specifically, esters such as polyhydric alcohol esters, phosphoric acid esters, and phthalic acid esters, linear paraffinic hydrocarbons, paraffinic hydrocarbons having a side chain, and paraffinic having an ester bond in the chain. Preferred are hydrocarbons, paraffinic hydrocarbons having a carbonyl group in the chain, and the like. Among them, it is particularly preferable to use diethylene glycol dibenzoate, tributyl phosphate, dimethyl phthalate, dibutyl phthalate, etc., which have good compatibility with the fixing layer.

FIG. 1 is a structural explanatory view of an example of a recording head of a printer for performing recording on a recording medium of the present invention. In FIG. 1, a recording head 1 of a printer includes a base 7.
And a protective plate 6 disposed thereon, a base 7 including a spacer disposed between the base 7 and the protective plate 6, and a spacer 7a.
c is formed, and the upper end of the recording liquid chamber is
A porous structure (small column) 5 for flying recording liquid droplets is provided below the opening end of the recording liquid chamber 10 which opens toward the recording liquid droplet flying chamber 10b formed in the above. The porous structure 5 is disposed, and a heating source (laser light source) 9
As a result, the recording liquid is heated via the condenser lens 8, and the heated recording liquid becomes droplets 10a and flies through the recording liquid droplet flight chamber. The recording medium 2 is composed of a support 3 and a recording liquid fixing layer 4 formed on one surface of the recording medium 2. So that the recording liquid droplet 10a
Adheres to the surface of the recording liquid fixing layer through the recording liquid droplet flight chamber 10b to form a desired image.

[0029]

The present invention will be described in more detail with reference to the following Examples, but it should be understood that the present invention is by no means restricted by such specific Examples. In the examples, "parts" means "parts by weight of solid content" excluding water, unless otherwise specified. "Recording Apparatus" A recording apparatus having a recording head shown in FIG. 1 (each side length and interval of a small column was 2 μm and height was 10 μm) was used. "Recording ink (cyan)"-Disperse dye: 10 parts of crystal violet-Medium: 90 parts of diethylene glycol dibenzoate (freezing point: 29 ° C or less, boiling point: 230 ° C)

Example 1 A high-quality paper (product name: Marshmallow; manufactured by Oji Paper Co., Ltd., basis weight 105 g / m ² ) having excellent whiteness and surface smoothness was used as a support. Was applied so that the dry weight was 18 g / m ^2, and dried to obtain a recording medium. (Coating solution for fixing layer: 20% concentration aqueous dispersion) Montmorillonite group mineral: Synthetic smectite (trade name: SWN Corp Chemical Co., Na _0.33 (Mg _2.67
1. Li _0.33 ) 30 parts of Si ₄ O ₁₀ (OH) ₂ , water dispersibility) Binder resin: 70 parts of polyester resin emulsion (trade name: HYTECPE-1010, glass transition temperature 50 ° C, particle size 60 nm, manufactured by Toho Chemical)

Example 2 A recording medium was obtained in the same manner as in Example 1 except that the following coating solution for a fixing layer was used. (Coating solution for fixing layer: 20% concentration aqueous dispersion) 1. Montmorillonite group mineral: 30 parts of synthetic smectite (trade name: manufactured by SWN Corp Chemical) Binder resin: polyester resin emulsion (glass transition temperature 50 ° C, trade name: HYTEC PE-
1010 Toho Chemical Co., Ltd. 60 parts, ethylene-vinyl acetate copolymer resin (trade name: Sumikaflex 473 Sumitomo Chemical Co., Ltd.) 10 parts

Example 3 A recording medium was obtained in the same manner as in Example 1 except that the following coating solution for a fixing layer was used. (Coating solution for fixing layer: 30% concentration aqueous dispersion) Montmorillonite Group Mineral: Synthetic smectite (trade name: SAN Corp Chemical Co., Na _0.33 (Mg _2.67
Li _0.33 ) Si ₄ O ₁₀ (OH) ₂ Synthetic smectite, SWN having non-polar organic solvent dispersibility) 2
0 parts, 2. 2. Pigment: 10 parts of calcined kaolin (trade name: Ansilex oil absorption: 90 ml / 100 g); Binder resin: polyester resin emulsion (glass transition temperature 50 ° C, trade name: HYTEC PE-
1010 Toho Chemical Co., Ltd. 60 parts, ethylene-vinyl acetate copolymer resin (trade name: Sumikaflex 473 Sumitomo Chemical Co., Ltd.) 10 parts

Example 4 A recording medium was obtained in the same manner as in Example 1 except that the following coating solution for a fixing layer was used. (Coating solution for fixing layer: 20% concentration aqueous dispersion) Montmorillonite group mineral: Synthetic smectite (trade name: Na _0.33 (Mg _2.67 manufactured by SPN Corp Chemical)
1. Li _0.33 ) Si ₄ O ₁₀ F ₂ ) 20 parts 2. Pigment: 10 parts of calcined kaolin (trade name: Ansilex oil absorption: 90 ml / 100 g); Binder resin: polyester resin emulsion (glass transition temperature 50 ° C, trade name: HYTEC PE-
1010 Toho Chemical Co., Ltd. 60 parts, ethylene-vinyl acetate copolymer resin (trade name: Sumikaflex 473 Sumitomo Chemical Co., Ltd.) 10 parts

Example 5 A recording medium was obtained in the same manner as in Example 1 except that the following coating solution for a fixing layer was used. (Coating solution for fixing layer: 20% concentration aqueous dispersion) 1. Montmorillonite group mineral: 29 parts of synthetic smectite (trade name: manufactured by SWN Corp Chemical) 2. Nonionic surfactant: 1 part of polyoxyethylene alkyl phenyl ether (trade name: Neugen EA120 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Binder resin: polyester resin emulsion (glass transition temperature 50 ° C, trade name: HYTEC PE-
1010, Toho Chemical Co.) 60 parts, ethylene-vinyl acetate copolymer resin (trade name: Sumikaflex 473, Sumitomo Chemical) 10 parts

Example 6 After a fixing layer was provided in the same manner as in Example 1, a gloss layer coating solution having the following composition was applied on the fixing layer so as to have a dry weight of 5 g / m ^2. A recording medium provided with a glossy layer by performing a smoothing process was prepared. (Coating liquid for gloss layer: 15% concentration aqueous dispersion) Fine pigment: colloidal silica (trade name: Snowtex C, manufactured by Nissan Chemical Industries, particle size: 10 nm to 20 nm) 60
Part, 2. 2. Nonionic surfactant: 0.5 part of polyoxyethylene alkyl phenyl ether (trade name: Neugen EA120 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Binder resin: polyester resin emulsion (trade name: HYTECPE-1010, manufactured by Toho Chemical)
40 parts

[0036]Comparative Example 1 On the support used in Example 1, the following coating solution for a fixing layer was applied.
20 g / m dry weight ^TwoCoated, dried and coated
I got a copy. (Coating solution for fixing layer: 20% concentration aqueous dispersion) Pigment: calcium carbonate (trade name: Brilliant-1)
5 30 Shiraishi Kogyo) 30 parts, Binder resin: polyester resin emulsion
(Product name: HYTECPE-1010, manufactured by Toho Chemical)
0 copies

[0037]Comparative Example 2 On the support used in Example 1, the following coating solution for a fixing layer was applied.
20 g / m dry weight ^TwoCoated, dried and coated
I got a copy. (Coating solution for fixing layer: 20% concentration aqueous dispersion) Pigment: amorphous silica (trade name: Fine Seal X-
1. 45 parts manufactured by Tokuyama) Binder resin: polyester resin (trade name: PE
-1010, manufactured by Toho Chemical) 70 parts

[0038]Comparative Example 3 On the support used in Example 1, the following coating solution for a fixing layer was applied.
20 g / m dry weight ^TwoCoated, dried and coated
I got a copy. (Coating solution for fixing layer: 20% concentration aqueous dispersion) Pigment: calcined kaolin (trade names: Ansilex, D
Ngelhard oil absorption 90ml / 100g) 3
0 parts, 2. Binder resin: polyester emulsion (gala
Transition temperature 50 ° C, trade name: HYTEC PE-101
0 Toho Chemical Co.) 60 parts, ethylene-vinyl acetate copolymer
Body resin (trade name: Sumika Flex 473 Sumitomo Chemical)
10 parts

Comparative Example 4 The support used in Example 1 was directly used as a recording medium.

Comparative Example 5 A glossy recording medium was obtained in the same manner as in Example 6, except that the fixing layer used in Comparative Example 1 was used instead of the fixing layer used in Example 6.

Evaluation Items (Recording Density) The optical density of the solid recording portion was measured with a Macbeth densitometer (RD-914, manufactured by Macbeth). (Ink Absorbency) Solid recording was performed twice on the same portion of the sample, and the recording portion was immediately rubbed with a cotton swab at a load of 100 g / cm ² , and the ink absorbency was checked by the degree of ink transfer to the cotton swab. ：: Absorbed sufficiently without sticking to cotton swabs. X: This is a level at which there is some adhesion to the cotton swab, which poses a problem in practical use. (Recording section preservability) After the recording sample was stored at 50 ° C. for 5 days, the recording density was measured, and the density maintenance rate (%) was determined. (Recording part bleeding) Bleeding of the recorded sample was visually determined one day after recording. A: Bleeding is hardly observed. ：: Slight bleeding is observed. ×: Bleeding is observed. XX: The bleeding is remarkable and is not practical. (Light fastness) After storing the recorded sample in a fade meter (60 ° C., 50% RH, 0.75 W / m ² , 24 hours)
The recording density was measured, and the density maintenance rate (%) was determined. Table 1 summarizes the evaluation results.

[0042]

[Table 1]

[0043]

According to the present invention, there is provided a recording medium and a recording method which are excellent in recording density, image quality and preservability, and provide a clear image without bleeding.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating an example of an apparatus for performing recording on a recording medium according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Recording head 2 ... Recording medium 3 ... Support 4 ... Recording liquid fixing layer 5 ... Porous structure 6 ... Protective plate 7 ... Base 7a ... Spacer 8 ... Condensing lens 9 ... Heat source 10 ... Recording liquid 10a ... Recording liquid droplet 10b: Recording liquid droplet flight chamber 10c: Recording liquid chamber

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masayuki Kamei 1-10-6 Shinonome, Koto-ku, Tokyo Inside Oji Paper Co., Ltd. Shinonome Research Center (72) Inventor Hiromasa Kondo 1-10-10, Shinonome, Koto-ku, Tokyo No. 6 Oji Paper Co., Ltd. Shinonome Research Center F term (reference) 2H086 AA04 AA13 AA34 AA42 AA48 BA03 BA14 BA16 BA21 BA31 BA33 BA34 DA06 DA17 DA27 2H111 AA01 AA08 AA27 AA31 AA32 AA47 CA02 CA03 CA23 CA30 CA33 HA00 HA12 HA24

Claims (8)

[Claims] 1. A recording liquid containing a recording material and a medium for dissolving or dispersing the recording material is supplied to a recording liquid flying means comprising a porous structure, and the recording liquid is vaporized by heating. A recording medium used in a recording method for sublimation or sublimation or formation of fine droplets, and transferring and adhering them to a recording medium disposed opposite to the recording liquid flying means, comprising: a support; And a fixing layer containing a montmorillonite group mineral. 2. The montmorillonite group mineral has the following composition formula (1): (X, Y) _2-3 Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (W
_1/3 ) (where, in the formula (1), X is Al, Fe (III), Mn
(III) or Co (III), where Y is Mg, Fe (I
I), represents Ni, Zn or Li, where Z is Si or Al
W represents K, Na or Ca, H ₂ O represents interlayer water, and m represents 0 or an integer of 1 or more. 2. The recording medium according to claim 1, wherein 3. A glossy layer containing a thermoplastic polymer substance and a fine pigment is further provided on the fixing layer.
Or the recording medium according to 2. 4. The thermoplastic polymer substance of the gloss layer includes at least one selected from a polyester resin and an acrylic resin, and the fine pigment of the gloss layer is
The recording medium according to claim 3, having an average particle diameter of 1.0 µm or less. 5. The fine pigment of the glossy layer according to claim 4, wherein the fine pigment contains at least one selected from aluminosilicate, amorphous silica, colloidal silica, calcined kaolin, diatomaceous earth, and urea-formaldehyde resin particles. Object to be recorded. 6. The recording medium according to claim 1, wherein the fixing layer contains a binder resin and a porous pigment together with the montmorillonite group mineral. 7. The recording medium according to claim 1, wherein the fixing layer further contains a surfactant. 8. The recording medium according to claim 1, wherein a recording liquid containing a recording material and a medium for dissolving or dispersing the recording material is formed of a porous structure. The recording liquid is supplied to a recording liquid flying means, and the recording liquid is vaporized by heating, sublimated or converted into fine droplets.
A recording method, wherein the recording liquid is transferred to and adhered to a recording medium arranged opposite to the recording liquid flying means.