JP2880258B2 - Manufacturing method of color prints - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a color print which is useful as a display for posters, signboards, etc., and in particular, the surface of the color print has excellent scratch strength and excellent water resistance. Related to color prints.

(Prior Art) Conventionally, a recording material having at least an ink holding layer and an ink transport layer on a support has been disclosed in JP-A-62-140878.
And a recording method using the same is described in JP-A-62-142680.

Although it is not impossible to observe a recorded image from a surface recorded with ink like ordinary paper on a recording material formed by these recording materials, the surface opposite to the recording surface, that is, the support surface side Various effects can be exhibited by observing the recorded image from. For example, post-processing such as lamination of the recorded image surface is unnecessary, and the image surface has appropriate gloss, high image density, and excellent recorded image clarity and light fastness. I can do it. Therefore, the recorded matter formed by these recording materials is used alone,
It is also useful to use it as a color print supported (adjacent or adhered, etc.) to another base such as a wall or window in a building or a panel board of various materials.

(Problems to be Solved by the Invention) However, since the ink transport layer surface side (back side) of a color print produced using the above-described specific recording material is porous, the strength is inferior, and nails, etc. However, there is a disadvantage that the surface of the ink transport layer is easily scratched by the scratching, and there is a problem that attention must be paid to the handling.

Furthermore, although the light-transmitting substrate side of the color print has excellent water resistance, the recording agent (dye or pigment contained in the ink) on the ink transport layer side slightly oozes out with water and stains the image. There was also the problem of water resistance.

Therefore, a first object of the present invention is to solve the above-mentioned problems and to provide a recording medium in which an image is formed with ink on a recording material having at least an ink holding layer and an ink transport layer on a light-transmitting substrate. It is an object of the present invention to provide a color print in which the surface strength of the object is improved and the handling of the recorded object is easy.

Further, a second object of the present invention is to provide a color print excellent in environmental resistance which can exhibit sufficient water resistance even when the color print is exposed to the outdoors.

(Means for Solving the Problems) The above object is achieved by the present invention described below.

In other words, the present invention provides a recording material in which at least an ink holding layer and an ink transport layer are sequentially provided on a light-transmissive substrate, by applying ink to the ink transport layer and passing the ink through the ink transport layer. A method for producing a color print, comprising forming an image on an ink holding layer, and then impregnating the ink transport layer surface with at least one resin.

(Function) By impregnating the ink transport layer of a recorded material having an image formed with ink droplets on a specific recording material with a resin, the strength of the porous ink transport layer can be improved.

Also, by appropriately selecting the resin to be impregnated, excellent water resistance can be imparted to the color print.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to preferred embodiments of the present invention.

The recording material used in the present invention includes a translucent base material as a support, an ink holding layer formed on the base material that substantially absorbs and captures ink or a recording agent, and an ink holding layer. And an ink transporting layer formed thereon and directly receiving ink and having liquid permeability.

Further, as a preferred embodiment for improving the liquid permeability of the ink transport layer, an example in which the ink transport layer has a porous structure having cracks and communication holes inside the ink transport layer is given.

In order to satisfy the above characteristics, it is preferable that the ink transport layer is mainly composed of particles that are not dyeable to the recording agent and a binder.

The non-staining particles used here may be single particles called primary particles or porous particles called secondary particles obtained by aggregating these.

Particularly preferred among these are porous particles, having a particle diameter of 0.01%.
２2 μm, preferably 0.05-1 μm, more preferably 0.1 μm.
Fine particles having a size of 1 to 0.5 μm aggregate to 0.1 to 30 μm,
The particles preferably have a size of 2 to 20 μm, more preferably 3 to 10 μm. Such secondary and tertiary aggregated porous particles do not easily disperse or separate.

Examples of such particles include polystyrene, polymethacrylate, elastomer, ethylene-vinyl acetate polymer, styrene-acryl copolymer, polyester,
Organic materials such as polyacryl, polyvinyl ether, polyamide, polyolefin, polysilicone, guanamine resin, polytetrafluoroethylene, SBR, urea resin, urea-formalin resin, or, for example, synthetic silica,
Clay, talc, diatomaceous earth, calcium carbonate, titanium oxide, zinc oxide, satin white, ammonium silicate,
At least one kind of particles of inorganic materials such as lithopone, aluminum hydroxide and calcium silicate can be used.

Next, the binder, which is another substance forming the ink transport layer, has a function of binding the above-mentioned particles to each other and / or the ink transport layer and the ink holding layer. It is preferably non-staining.

As the material preferable as the binder, any conventionally known materials can be used as long as they have the above functions.
For example, polyvinyl alcohol, acetal-modified polyvinyl alcohol, ion-modified polyvinyl alcohol, acrylic resin, styrene-acryl copolymer, polyvinyl acetate, polyurethane, ethylene-vinyl acetate copolymer,
One or more of starch, polyvinyl acetal, gelatin, casein, ionomer, gum arabic, carboxymethyl cellulose, polyvinyl pyrrolidone, polyacrylamide, phenolic resin, melamine resin, epoxy resin, SBR, urea resin, olefin resin, chloroprene rubber, nitrile rubber, etc. Can be used.

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

In the present invention, various additives such as a surfactant, a penetrant, a fluorescent dye, a coloring agent, and a crosslinking agent may be added to the ink transport layer as needed to further improve the function as the ink transport layer. May be appropriately added.

The thickness of the ink transport layer is preferably in the range of 5 to 150 μm, more preferably in the range of 10 to 50 μm.

Next, the ink holding layer, which constitutes the recording material together with the ink transport layer, has a higher ink absorbing power than the ink transport layer in order to stably absorb and capture the ink temporarily absorbed by the ink transport layer. You need to be strong.

Further, in the color print of the present invention, since the recorded image is observed from the side opposite to the recording surface as described above, the ink holding layer is preferably transparent.

Therefore, in order to satisfy these functions, the ink holding layer may be mainly composed of a light-transmitting resin that adsorbs the recording agent and / or a light-transmitting resin that is soluble or swellable in the ink. preferable.

For example, when an aqueous ink containing an acidic dye or a direct dye is used as a recording agent, the ink holding layer is made of a resin having an adsorptive property for the dye, for example, a water-soluble resin having a swelling property for an aqueous ink. It is preferable to be composed of a hydrophilic or hydrophilic polymer.

Such water-soluble or hydrophilic polymers include, for example, natural resins such as albumin, gelatin, casein, starch, cationic starch, gum arabic, and sodium alginate;
Carboxymethylcellulose, hydroxyethylcellulose, polyamide, polyacrylamide, polyethyleneimine, polyvinylpyrrolidone, quaternized polyvinylpyrrolidone, polyvinylpyridium halide, melamine resin, phenolic resin, alkyd resin, polyurethane, acetal-modified polyvinyl alcohol, ion-modified polyvinyl alcohol, polyvinyl Alcohol, polyester, synthetic resin such as sodium polyacrylate, preferably,
Examples thereof include a hydrophilic polymer made by crosslinking these resins to make them water-insoluble, a hydrophilic and water-insoluble polymer complex composed of two or more resins, a hydrophilic and water-insoluble polymer having a hydrophilic segment, and the like.

The thickness of the ink holding layer formed using the above material is preferably in the range of 1 to 30 μm, more preferably 3 to 10 μm.

As the light-transmitting substrate used in the present invention, any conventionally known materials can be used, and specific examples thereof include a resin film such as polyester and a glass plate.

As a method of forming the ink holding layer and the ink transport layer on the translucent substrate, a coating solution is prepared by dissolving or dispersing the above-mentioned materials in an appropriate solvent, and the coating solution is ,
For example, a method in which the composition is applied onto a light-transmitting substrate by a conventionally known method such as a roll coating method, a rod bar coating method, an air knife coating method, and the like, and then dried quickly is preferable. Further, the above-mentioned material may be a hot-melt coating method or a method of once forming a single sheet from the above-mentioned material and then laminating the sheet to a substrate.

However, when providing the ink holding layer on the translucent substrate,
For example, it is preferable that the adhesion between the base material and the ink holding layer is strengthened by a method such as forming an anchor coat layer to eliminate voids. If there is a gap between the base material and the ink holding layer, the surface of the recorded image is irregularly reflected, which substantially lowers the optical density of the image, which is not preferable.

The color recorded matter used in the present invention is one in which an image is formed using the above-described recording material, and as a means for forming a color image using these recording materials, a fountain pen, a ballpoint pen, a felt pen, Examples include a recording apparatus and a recording apparatus using an ink containing a recording agent (a dye, a pigment, and the like), such as a pen plotter and an ink jet. Among these, the inkjet recording method is preferable from the viewpoint of high-speed image recording.

As the ink used in the above, a conventionally known water-based and / or oil-based ink can be used, but the ink is promptly penetrated into the ink transport layer of the recording material, and is quickly absorbed by the ink holding layer. In order to capture the ink, the viscosity of the ink is preferably 100 cps or less, more preferably 50 cps or less. In consideration of fire safety and environmental impact, water-based inks are preferred.

Further, as a recording agent to be contained in the ink, a conventionally known material having a coloring agent such as a dye, a pigment, a pigment and the like and a coloring agent can be used. For example, as a recording agent used for ink jet recording, a direct dye, a basic dye, a reactive dye, and a water-soluble dye represented by an edible dye are preferable.

As the resin to be impregnated in the ink transport layer of the recorded matter formed in this way, a polymer compound that can be impregnated on the surface or inside of the ink transport layer as a solution or a dispersion liquid that does not deteriorate over time is preferable.

For example, vinyl acetate, vinyl chloride, vinylidene chloride,
Polymers and copolymers such as acrylate, styrene, acrylonitrile, ethylene, butadiene, polyester, polyamide, melamine resin, urea resin, phenol resin, alkyd resin, polyurethane, epoxy resin, polyvinyl butyral, SBR, rosin, rosin ester , Nitrocellulose, acetylcellulose, ethylcellulose, chlorinated paraffin, liquid paraffin, paraffin wax, polybutene, polybutadiene, α-olefin oligomer, polyhydroxypolyolefin and the like.

Furthermore, water-soluble resins such as polyvinyl alcohol, polyvinylpyrrolidone, gelatin, casein, starch, carboxymethylcellulose, and styrene-maleic anhydride copolymer can also be used. Among these, a resin that is soluble in a volatile organic solvent and has a low viscosity is preferable from the viewpoint of quick drying.

A resin selected from these materials is impregnated in the form of a solution, dispersion, or emulsion from the ink transport layer side of the color recording.

At this time, any solvent or dispersion medium can be used, but an organic solvent which is insoluble in a recording agent is preferable in order not to cause bleeding of a color image. In addition, even if it is an organic solvent which is easily soluble in the recording agent, the effect on the recording agent is very small as long as the solvent has a high volatility, and it can be used.

The solution and / or dispersion containing the resin can be impregnated into the ink transport layer of a color print by a conventionally known method such as spray coating, a bar coater, a roll coater, a blade coater, and a gravure coater. In view of simplicity, impregnation by spray coating is most preferable.

Depending on the resin selected, the refractive index with the material of the ink transport layer becomes close, and the whiteness (or opacity) of the background of the original color print may not be maintained. In such a case, The resin solution and / or the dispersion contain fine particles having different refractive indices, thereby making it possible to supplement the whiteness (or opacity) of the background.

In addition, other various additives such as an antioxidant, a water repellent, a waterproofing agent, a coloring material, a preservative, and a fungicide may be mixed in the resin solution and / or dispersion liquid to be impregnated. I can do it.

The amount of resin impregnated on the ink transport layer surface is not particularly limited as long as the ink transport layer surface has sufficient strength.
About 85 g / m ² is preferable.

Incidentally, the impregnation of the ink transport layer surface of the color recording material with the resin can be carried out immediately after the image is recorded with the ink droplets on the recording material, but by the solvent in the ink on which the image is recorded. In order to avoid adverse effects, it is preferable to carry out the process after the ink is sufficiently dried. The drying of the ink can be carried out at 30 ° C. or higher, preferably at 80 ° C. or higher.

(Examples) Next, the present invention will be described more specifically with reference to reference examples, examples, and comparative examples.

In the description, parts and% are based on weight unless otherwise specified.

Reference Example 1 (Preparation of Recording Material) A 75 μm-thick polyethylene terephthalate film (manufactured by Toray Industries Inc.) was used as a light-transmitting substrate, and the following composition A was coated on this substrate so that the dry film thickness became 6 μm. Coating was performed with a bar coater, and the coating was dried at 140 ° C. for 7 minutes in a drying furnace.

Composition A Cation-modified polyvinyl alcohol (C-polymer, manufactured by Kuraray, 10% aqueous solution) 100 parts Block isocyanate (Elastron BN-5, manufactured by Daiichi Kogyo Seiyaku) 2.5 parts Organotin-based compound (Elastron Catalyst 64, Daiichi Next, the following composition B was coated thereon with a bar coater so as to have a dry film thickness of 25 μm, and dried in a drying oven at 140 ° C. for 6 minutes.

Composition B Urea-formalin resin (organic filler, manufactured by Nippon Kasei Co., Ltd., particle size of about 5 μm) 100 parts acetal resin (Eslek KX-1, manufactured by Sekisui Chemical Co., Ltd.
8 parts solution) 500 parts Block isocyanate (Elastron BN-5, manufactured by Daiichi Kogyo Pharmaceutical) 50 parts Organotin compound (Elastron Catalyst 64, manufactured by Daiichi Kogyo Pharmaceutical) Trace amount sodium octyl sulfosuccinate 4 parts Isopropyl alcohol 500 parts Water 100 parts The recording material of Reference Example 1 thus obtained was white and opaque.

Reference Example 2 (Formation of Color Image) Using a color inkjet printer (BJC-440, manufactured by Canon), black, yellow, magenta, cyan, blue (magenta + cyan), Solid recording of seven colors of green (cyan + yellow) and red (yellow + magenta) was performed.

The recorded matter obtained in this manner has a higher image density on the opposite side than the image density on the ink transporting layer side which is the image recording surface, that is, the image density on the light-transmitting substrate side which is the image observation surface. Was a color recorded matter having an appropriate gloss.

Example 1 A 10% acetone solution of a butyral resin (Eslec BX-1, manufactured by Sekisui Chemical Co., Ltd., molecular weight: 100,000) was coated on the surface of the ink transport layer of the color record obtained in Reference Example 2 using a bar coater. Dried at ℃ 3 minutes (resin impregnation amount is 15g /
m ^2).

Example 2 An ethyl acetate solution of an acrylic resin (Dianal BR-105, manufactured by Mitsubishi Rayon Co., Ltd., molecular weight: 55,000) was applied to the surface of the ink transport layer of the color recording obtained in Reference Example 2 by a spray method (resin). The impregnation amount is 12 g / m ² ).

Example 3 An ethyl acetate solution of a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd., molecular weight: 17,000) was applied to the surface of the ink transport layer of the color record obtained in Reference Example 2 with a bar coater (resin impregnation amount). Is 16 g / m ² ).

Example 4 An aqueous solution of hydroxyethyl cellulose (average degree of polymerization: 750) was applied to the surface of the ink transport layer of the color record obtained in Reference Example 2 using a bar coater (resin impregnation amount: 20 g /
m ^2).

Example 5 Completely saponified polyvinyl alcohol (average degree of polymerization: 170) was applied to the surface of the ink transport layer of the color recorded matter obtained in Reference Example 2.
0) aqueous solution was coated with a bar coater (resin impregnation amount is 2
0g / m ^2).

Comparative Example 1 The color recorded matter obtained in Reference Example 2 was used without resin impregnation.

The color prints of the respective Examples and Comparative Examples obtained as described above were tested and evaluated according to the following methods to determine whether or not the color prints were sufficiently suitable for the purpose of the present invention. The evaluation results are shown in Table 1.

[I] Image recording density (OD) is measured by Macbeth densitometer RD-91
Using No. 8, the measurement was carried out for each of the black, yellow, magenta and cyan ink recording portions from the light-transmitting substrate surface side (A) and the ink transport layer surface side (B) of the color recorded matter.

[II] The ink transport layer surface strength was evaluated as x when the ink transport layer surface was scratched with a nail and the ink transport layer was damaged, and as o when the ink transport layer was not damaged.

[III] For water resistance, the color print was dipped in tap water at 20 ° C, immediately pulled out and dried at 100 ° C. The color image viewed from the light-transmitting substrate side was visually observed, and those with dirt on the image were evaluated as x, those that were slightly recognized but had no effect on the image were evaluated as Δ, and those that were not recognized were evaluated as o. did.

[IV] The overall evaluation was evaluated as good when the ink transporting layer surface strength and water resistance of the color recorded matter were satisfied, and as poor when the other conditions were satisfied.

(Effects of the Invention) As described above, according to the present invention, the scratching strength on the ink transport layer surface side of a color recorded matter on which a color image is formed using a specific recording material is improved, and the handleability is improved.

In addition, the water resistance of the color print is improved, and the color print can be used outdoors, and the use of the color print is wide.

Claims (14)

(57) [Claims] An ink is applied to an ink transport layer on a recording material having at least an ink holding layer and an ink transport layer sequentially provided on a light-transmitting substrate, and the ink is passed through the ink transport layer. A method for producing a color print, comprising: forming an image on a holding layer; and then impregnating the surface of the ink transport layer with at least one resin. 2. The method according to claim 1, wherein the image is formed by an ink jet recording method using an aqueous ink. 3. The method for producing a color print according to claim 1, wherein the resin is impregnated using a resin solution containing an organic solvent. 4. The resin according to claim 1, wherein said resin is vinyl acetate, vinyl chloride, vinylidene chloride, acrylate, styrene, acrylonitrile, ethylene, butadiene, polyester, polyamide, melamine resin, urea resin, phenol resin,
Alkyd resin, polyurethane, epoxy resin, polyvinyl butyral, styrene-butadiene rubber, rosin, rosin ester, nitrocellulose, acetylcellulose, ethylcellulose, paraffin chloride, liquid paraffin, paraffin wax, polybutene, polybutadiene, α-olefin oligomer, polyhydroxypolyolefin 2. The method for producing a color print according to claim 1, wherein the method is selected from polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, casein, starch, carboxymethyl cellulose, and styrene-maleic anhydride copolymer. 5. The method according to claim 1, wherein the impregnation amount of the resin is in the range of ² to 85 g / m ² . 6. The method according to claim 1, wherein the resin is impregnated after the applied ink is dried. 7. The method according to claim 1, wherein the ink transporting layer has a white color. 8. The method for producing a color print according to claim 1, wherein the ink transport layer contains non-dying particles and a binder. 9. The method according to claim 8, wherein the size of the non-dying particles is in the range of 0.1 to 30 μm. 10. The weight ratio of the non-dying particles and the binder is from 10/1 to 10/1.
The method for producing a color print according to claim 8, wherein the color print is in a range of 1/2. 11. The method according to claim 1, wherein the thickness of the ink transport layer is in the range of 5 to 150 μm. 12. The method for producing a color print according to claim 1, wherein the ink holding layer has translucency. 13. The method for producing a color print according to claim 1, wherein the ink holding layer contains a light-transmitting resin that adsorbs a dye. 14. The method according to claim 1, wherein the thickness of the ink holding layer is in the range of 14 to 30 μm.