JPH0459281A - Material to be recorded - Google Patents

Abstract

PURPOSE:To manufacture a material to be recorded and having a pearl-like gloss without loss of recording characteristics of a specific original material to be recorded by incorporating a specific amount or more of pearl pigment in an ink transport layer. CONSTITUTION:A material to be recorded is composed of a light transmission base material as a support, an ink holding layer formed on the base material for substantially absorbing and collecting ink or recording agent, and an ink transport layer formed on the holding layer for directly receiving the ink and having liquid permeability. As a preferable aspect of improving the liquid permeability of the transport layer, an example of an ink transport layer of a porous structure having a crack, a communicating hole in the transport layer is provided. The transport layer is formed mainly of nondying particle to the agent and a binder. The content amount of pearl pigment into the transport layer depends upon the type, shape, size of the pigment to be contained and the thickness of the transport layer. If it is included only in the transport layer, the content of the pigment in the transport layer is desirably 15wt.% or more. If it is less than 15wt.%, pearl gloss might not be exhibited.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a recording material for producing color prints useful as displays such as posters and signboards, and particularly relates to a recording material for producing color prints useful as displays such as posters and signboards. The present invention relates to a recording material that forms an image with ink on the recording material that has an ink retaining layer and an ink transport layer.

(Prior Art) Conventionally, a recording material having at least an ink retaining layer and an ink transport layer has been described in Japanese Patent Application Laid-Open No. 140878/1987, and a recording method using the same has been described in Japanese Patent Application Laid-Open No. 140878. It is described in Publication No. 142680/1983.

Although it is not impossible to observe the recorded image from the side recorded with ink on the recorded matter formed by these recording materials, like ordinary paper, it is possible to observe the recorded image from the side recorded with ink, By observing the recorded image from the body side, there is no need for post-processing such as lamination of the image surface, and the image surface has a moderate gloss, high image density, and excellent clarity and light resistance. It can be done.

Therefore, in addition to using such recorded materials alone, it is also useful to use them as color prints supported (adjacent, glued, etc.) on other substrates such as walls and windows in buildings, or panel boards made of various materials. It is.

In addition, in order to expand the use of these color prints made using recording materials having at least an ink retention layer and an ink transport layer, Japanese Patent Application Laid-Open No. 64-55276,
JP-A-64-56583, JP-A-1-12248
No. 1 and JP-A-1-159286 disclose the inclusion of a pearl pigment as an additive in the ink retaining layer and the ink transport layer.

Furthermore, pearl pigment coated paper manufactured by coating with pearl pigment is disclosed in Japanese Patent Publication No. 38-29267.
No. 1-47597.

(The problem that the invention is trying to solve) However,
The recording materials described in the above-mentioned publications, which have at least an ink retention layer and an ink transport layer, do not contain detailed descriptions of the type and content of pearl pigments, and the inherent recording properties of the recording materials are not described in detail. It has not been possible to provide a recording material that has a suitable pearlescent luster without damaging it.

Furthermore, the pearl pigment-containing paper found in the conventional pearl pigment-coated paper in each of the above-mentioned publications has a large difference in structure and image forming method from the recording material of the present invention. It was difficult to apply it to wood.

Therefore, an object of the present invention is to solve the above-mentioned problems, and to provide a recording material having at least an ink retaining layer and an ink transport layer on a transparent substrate, without impairing the original recording properties of the recording material. An object of the present invention is to provide a recording material having excellent pearlescent luster.

(Means for solving problems) The above objects are achieved by the present invention as described below.

That is, in the present invention, when recording with ink on a recording material having at least an ink retaining layer and an ink transport layer on a transparent base material, the image density measured from the side of the transparent base material is higher than that of the ink transport layer. A recording material having an image density higher than that measured from the side, wherein the ink transport layer contains 15% by weight or more of a pearl pigment, and at least an ink on a transparent substrate. When recording with ink on a recording material having a retention layer and an ink transport layer, the image density measured from the transparent substrate side is higher than the image density measured from the ink transport layer side. , the light-transmitting base layer and/or the ink-retaining layer contains a pearl pigment, and the total light transmittance of the laminate of the light-transmitting base layer and the ink-retaining layer is 60 to 88%. This is a recording material characterized by:

(Function) According to the present invention, by specifying the optimum content of pearl pigment for the specific recording material, it is possible to record a pearly luster without impairing the inherent recording properties of the specific recording material. material can be manufactured.

In addition, a recorded material in which an image is formed with ink using the recording material has excellent pearlescent luster without impairing the original recording characteristics.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

The pearl pigments that primarily characterize the present invention include natural pearl essence obtained by finely pulverizing conventionally known fish scales;
Mica powder or synthetic pearl pigments such as basic lead carbonate, bismuth trichloride, or titanium oxide coated mica powder can be used.

The content of the pearl pigment in a specific recording material having at least an ink retaining layer and an ink transport layer on a light-transmitting substrate cannot be limited because it varies depending on the type and shape of the pearl pigment. The maximum limit is the point where the image density on the transparent substrate side is lower than the image density on the ink transport layer side when the recording material is recorded with ink.

The above pearl pigment is contained in any layer of the transparent base material, the ink holding layer and the ink transport layer.
Fine particles with a size of 2 μm, preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm aggregate to form a particle size of 0.1 μm.
The particles have a size of ~30 μm, preferably 2-20 μm, more preferably 3-10 μm. These secondary and tertiary agglomerated porous particles are easily dispersed and
It cannot be separated.

Examples of such particles include polystyrene, polymethacrylate, elastomer, ethylene-vinyl acetate polymer, styrene-acrylic copolymer, polyester, polyacrylic, polyvinyl ether, polyamide, polyolefin, polysilicone, guanamine resin, polytetra Organic materials such as fluoroethylene, 5BR1 urea resin, urea-formalin resin, or, for example, synthetic silica,
Clay, talc, diatomaceous earth, calcium carbonate, titanium oxide, zinc oxide, satin white, aluminum silicate,
Particles of at least one kind of inorganic materials such as lithopone, aluminum hydrochloride, and calcium silicate are used.

Next, the binder, which is another substance forming the ink transport layer, has the function of binding the particles and/or the ink transport layer and the ink retention layer, and is used for recording in the same way as the particles. It is preferable that the material is non-staining with respect to the agent.

As a preferable material for the binder, any conventionally known material can be used as long as it has the above-mentioned functions, such as polyvinyl alcohol, acrylic resin, styrene-acrylic copolymer, polyvinyl acetate, polyurethane,
Ethylene-vinyl acetate copolymer, starch, modified polyvinyl alcohol, gelatin, casein, ionomer, gum arabic, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylamide, phenolic resin, melamine resin, epoxy resin, 5BR1 urea resin, olefin resin, chlorobrene One or more of rubber, nitrile rubber, etc. can be used.

The mixing ratio of the particles and the binder varies depending on the type and diameter of the particles, but is preferably in the range of 10/1 to 1/2, more preferably in the range of 5/1 to 1/1.

The content of the pearl pigment used in the present invention in the ink transport layer depends on the type, shape, and size of the pearl pigment to be contained and the thickness of the ink transport layer, but when it is contained only in the ink transport layer, It is preferable that the Burr pigment content in the ink transport layer is 15% by weight or more. If 15% by weight is not swirled, pearlescent luster may not be developed.

In addition, since pearl pigments are side-like and tend to inhibit the function of the ink transport layer, when using them, the amount of pearl pigments should be kept as low as possible, and the ink retention layer and/or translucency It is preferable to contain and use a base hevar pigment.

In the present invention, in order to further improve the function as an ink transport layer, various additives may be added as necessary, for example,
Surfactants, penetrants, fluorescent dyes, colorants, crosslinking agents, and the like may be added as appropriate to the ink transport layer.

The thickness of the ink transport layer varies depending on the amount of ink to be recorded, but is preferably 5 to 150 μm, more preferably 1 μm.
It is in the range of 0 to 50 μm.

Next, the ink retaining layer needs to have a stronger ink absorption ability than the ink transport layer in order to stably absorb and capture the ink temporarily absorbed by the ink transport layer.

Furthermore, in order to observe the recorded image from the side opposite to the recording surface as described above, the ink retaining layer is preferably translucent.

The ink retaining layer that satisfies the above-mentioned functions is preferably composed mainly of a light-transparent resin that adsorbs the recording agent and/or a light-transparent resin that is soluble or swellable with respect to the ink.

For example, when a water-based ink containing an acid dye or a direct dye is used as a recording material, the ink-retaining layer is made of a resin that has adsorption properties for the dye, such as a water-soluble or hydrophilic resin that has swelling properties for the water-based ink. It is preferable that the material is made of a polymer with a sterile property.

Examples of such water-soluble or hydrophilic polymers include:
Albumin, gelatin, casein, starch, cationic starch, gum arabic, natural resins such as sodium alginate, carboxymethylcellulose, hydroxyethylcellulose, polyamide, polyacrylamide, polyethyleneimine, polyvinylpyrrolidone, quaternized polyvinylpyrrolidone, polyvinylpyridium halide, melamine Synthetic resins such as resins, phenolic resins, alkyd resins, polyurethanes, acetal-modified polyvinyl alcohols, ion-modified polyvinyl alcohols, polyvinyl alcohols, polyesters, and sodium polyacrylates, preferably hydrophilic polymers made by crosslinking these resins to make them water-insoluble. , a hydrophilic and water-insoluble polymer complex consisting of two or more types of resins, a hydrophilic and water-insoluble polymer having a hydrophilic segment, and the like.

The content of the pearl pigment used in the present invention in the ink retention layer depends on the type, shape, and size of the pearl pigment to be included, as well as the thickness of the ink retention layer. Care must be taken to ensure that the image density on the transparent substrate side when formed as a material and recorded with ink is not lower than the image density on the ink transport layer side. A preferred method for checking this in advance is to measure the total light transmittance of the translucent base material and the ink retaining layer. An ink retaining layer containing a pearl pigment is laminated on a transparent substrate, and the total light transmittance is measured. The measured value is 60%
A range of 88% to 88% serves as a guideline for determining the pearl pigment content in the ink retaining layer.

That is, the content of pearl pigment is 60% of the above total light transmittance.
If it is less than this, the ink retaining layer loses its translucency, making it difficult to see the recorded image from the translucent substrate side, which is not preferable.

On the other hand, when the total light transmittance exceeds 88%, the degree of burl gloss when used as a recording material is small and the effect is small.

In addition, the total light transmittance as used in the present invention is JISK 67
14 Refers to those measured according to 4.5 light transmittance (however, the size of the test piece is arbitrary).

The thickness of the ink retaining layer formed using the above material varies depending on the amount of ink to be recorded, but is preferably 1 to 3.
The range is 0 μm, more preferably 3 to 10 μm.

As the translucent substrate used in the present invention, any conventionally known substrate can be used, and specific examples thereof include resin films such as polyester, glass plates, and the like.

The content of the pearl pigment used in the present invention in the translucent base material depends on the type, shape, and size of the pearl pigment contained and the thickness of the translucent base material, but in order to maintain the above-mentioned characteristics, When formed as a recording material and recorded with ink, care must be taken to ensure that the image density on the transparent substrate side does not fall below the image density on the ink transport layer side. A preferred method for checking this in advance is to measure the total light transmittance of a laminate of a translucent base material and an ink retaining layer. The range of the measured value from 60% to 88% serves as a guideline for determining the content of the pearl pigment in the translucent base material.

That is, the content of Burr pigment is 60% of the above total light transmittance.
If the total light transmittance exceeds 88%, the transparent substrate loses its translucency and the recorded image becomes difficult to see from the transparent substrate side (which is not preferable).On the other hand, if the total light transmittance exceeds 88%, When used as a recording material, the degree of emitting burl gloss is very small and the effect is small.

As a method for forming an ink retaining layer and an ink transport layer on the above-mentioned light-transmitting substrate, a coating solution is prepared by dissolving or dispersing the above-mentioned materials in an appropriate solvent, and this coating solution is ,
For example, it is preferable to apply the coating onto a substrate by a conventionally known method such as a roll coating method, a rod bar coating method, or an air knife coating method, and then quickly dry the coating. Alternatively, a hot melt coating method using the above material or a method in which a single sheet is formed from the above material and the sheet is laminated onto a base material may be used.

Further, when providing an ink retaining layer on a transparent substrate, the adhesion between the base material and the ink retaining layer can be strengthened by, for example, forming an anchor coat layer.

The recording material of the present invention forms an image using ink, and means for forming a color image using these recording materials include a fountain pen, a ballpoint pen, a felt-tip pen, a pen plotter, and an inkjet. Examples include recording instruments and recording devices that use ink containing a recording agent (pigment such as dye). Inkjet recording is preferred from the viewpoint of high-speed image recording.

As the ink used above, conventionally known water-based and/or oil-based inks can be used, but the ink quickly penetrates into the ink transport layer of the recording material and is quickly absorbed and captured by the ink retention layer. Therefore, the viscosity of the ink must be 10
It is preferably 0 cpS or less, more preferably 50
cps or less. In addition, water-based inks are preferred in consideration of fire safety and environmental impact.

Further, as the recording agent contained in the ink, a material containing a conventionally known coloring agent such as a dye or pigment and a coloring agent can be used. For example, as the recording agent used in inkjet recording, water-soluble dyes such as direct dyes, basic dyes, reactive dyes, and food colorings are preferred.

(Example) Next, the present invention will be described in more detail by giving examples and comparative examples. Note that parts or percentages in the text are based on weight unless otherwise specified.

100μm thick containing pearl pigment as implementation side transparent base material
Using a polyethylene terephthalate film, the following composition A was coated onto this base material using a bar coater so that the dry film thickness was 6 μm, and dried at 140° C. for 6 minutes in a drying oven.

Cosmetics A Cation-modified polyvinyl alcohol (C-polymer, manufactured by Kuraray, 10% aqueous solution) 100 parts Blocked isocyanate (Elastron BN-5, manufactured by Dai-Kogyo Seiyaku)
2.5 Organotin compound (Elastron Catalyst 64, manufactured by Dai-Kogyo Seiyaku)
Further, a small amount of Composition B below was applied thereon using a bar coater so that the dry film thickness was 25 μm, and the mixture was dried in a drying oven at 140° C. for 5 minutes.

Urea-formalin resin (organic filler, manufactured by Nippon Kasei, average particle size 5 μm) 100 parts acetatal resin (S-LEC KX-1, manufactured by Block Chemical Co., Ltd., 8% solution)
500 parts blocked isocyanate (
Elastron BN-5, manufactured by Dai-Kogyo Seiyaku)
50 parts Organotin compound (Elastron Catalyst 64, manufactured by Dai-Kogyo Seiyaku) Trace amount of sodium dioctyl sulfosuccinate 4 parts Isopropyl alcohol 500 parts Water
100 parts Example 2 Thickness 100μ with different Burl pigment concentrations as transparent base material
A recording material of Example 2 was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film of No. m was used.

Example 3 Thickness 100μ with different pearl pigment concentrations as transparent base material
A recording material of Example 3 was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film of No. m was used.

Comparative Example 1 Thickness 100μ with different pearl pigment concentrations as transparent base material
A recording material of Comparative Example 1 was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film of No. m was used.

Example 4 Thickness 100μ with different pearl pigment concentrations as transparent base material
A recording material of Example 4 was prepared in the same manner as in Example 1 except that a polyethylene terephthalate film of No. m was used.

Example 5 A polyethylene terephthalate film (manufactured by Toshi) with a thickness of 100 μm was used as a transparent base material, and the following composition C was coated on this base material using a bar coater so that the dry film thickness was 6 μm. It was dried in a drying oven at 140°C for 6 minutes.

Cation-modified polyvinyl alcohol (C-polymer, manufactured by Kuraray, 10% aqueous solution) 100 parts blocked isocyanate (Elastron BN-5, manufactured by Dai-Kogyo Seiyaku)
2.5 parts organotin compound (Elastron Catalyst 64, manufactured by Dai-Kogyo Seiyaku)
Further, 1.5 parts of a trace pearl pigment (Iriodin 120 manufactured by Merck Japan) was coated with the above composition B using a bar coater so that the dry film thickness was 25 μm, and the mixture was heated at 140°C in a drying oven.
and dried for 5 minutes.

Example 6 The amount of pearl pigment added in the composition C was 0. A recording material of Example 6 was prepared in the same manner as Example 5 except that 5 copies were used.

Example 7 A recording material of Example 7 was prepared in the same manner as in Example 5 except that the amount of pearl pigment added in the composition C was changed to 0.205 parts.

Comparative Example 2 A recording material of Comparative Example 2 was prepared in the same manner as in Example 5, except that the amount of pearl pigment added in Composition C was 2 parts.

Example 8 A recording material of Example 8 was prepared in the same manner as in Example 5, except that the amount of pearl pigment added in Composition C was 0.02 part.

Example 9 A polyethylene terephthalate film (manufactured by Toshi) with a thickness of 100 μm was used as a transparent base material, and the composition A was coated onto this base material using a bar coater so that the dry film thickness was 6 μm. It was dried in a drying oven at 140°C for 6 minutes.

Furthermore, the following composition was coated on top of it using a bar coater so that the dry film thickness was 25 μm, and the mixture was heated at 140°C in a drying oven.
and dried for 5 minutes.

Urea-formalin resin (organic filler, made by Nippon Kasei, average particle size 5 μm) 100 parts acetal resin (S-LEC KX-1, made by Block Chemical Co., Ltd., 8% solution)
500 parts blocked isocyanate (Elastron BN-5, manufactured by Dai-Kogyo Seiyaku)
500 parts Tin-based compound (Elastron Catalyst 64, Dai-Kogyo Seiyaku Co., Ltd.) Trace amount of sodium dioctyl sulfosuccinate 4 parts Pearl pigment (
Iriodin, manufactured by Merck Japan) 30 parts isopropyl alcohol 500 parts water
100 parts Comparative Example 3 A recording material of Comparative Example 3 was prepared in the same manner as in Example 9 except that the amount of pearl pigment added in the composition was 15 parts.

Comparative Example 4 A recording material of Comparative Example 4 was prepared in the same manner as in Example 1, except that a 100 μm thick polyethylene terephthalate film (manufactured by Toshi) was used as the transparent base material.

The recording materials of the above Examples and Comparative Examples were printed using a color inkjet printer (BJC-440, manufactured by Canon) to print black, yellow, magenta, cyan, blue (magenta + cyan), and green (cyan + yellow). , 7-color solid recording of red (yellow + magenta) was performed.

The color prints thus obtained were tested and evaluated in accordance with the following method to determine whether they were sufficiently suitable for the purpose of the present invention. The evaluation results are shown in Table 1.

(1) Image optical density (0,0,) is Macbeth Densitometer R
D-918 was used to record the magenta ink recording area on the transparent substrate side (A) and the ink transport layer side (B) of the color print.
).

(2) Image density ratio is the image optical density (A
) and (B) according to the formula below.

Concentration ratio = (A) / (B) (3) The total light transmittance (
Tt) was measured.

(4) The burl glossiness of a color recording is determined by visually observing the color recording from the translucent substrate side. Those with a clear burl gloss are marked as ○, and those with a slight burl gloss are marked as △.
The ones that are missing are marked as X.

(5) For the overall evaluation, recording materials that satisfied the above-mentioned recording properties and clearly had burl gloss were rated as ◯, those that had slight burl gloss were rated as △, and the others were rated as ×.

(The following is a margin) (Effects of the Invention) According to the present invention, it is possible to form a pearlescent color image even on the above-mentioned specific recording material without impeding the recording suitability of the ink, and it is suitable for use as a color recorded material. has spread.

Claims (2)

[Claims] (1) When recording with ink on a recording material having at least an ink retaining layer and an ink transport layer on a transparent substrate, the image density measured from the transparent substrate side is measured from the ink transport layer side. What is claimed is: 1. A recording material having an image density higher than that of an image, wherein the ink transport layer contains 15% by weight or more of a pearl pigment. (2) When recording with ink on a recording material that has at least an ink retention layer and an ink transport layer on a light-transparent base material, the image density measured from the light-transparent base material side is measured from the ink transport layer side. In the recording material whose image density is higher than that of the transparent base material layer and/or the ink retaining layer, the transparent base material layer and/or the ink retaining layer contain a pearl pigment, and the laminate of the transparent base material layer and the ink retaining layer is A recording material having a total light transmittance of 60 to 88%.