JPS61205182A - Multicolor recording material - Google Patents

Abstract

PURPOSE:To obtain a multicolor recording without intermixture of colors by utilizing different infrared rays by plurally laminating layers containing a developer for the color-forming substance in a mutually adjoining manner. CONSTITUTION:Layers 4a, 4b, and 4c containing substances 2a, 2b, and 2c to produce different colors and infrared rays absorbers 3a, 3b, and 3c having different max. absorption wavelengths are laminated alternately with layers 6a and 6b containing developers 5a and 5b to produce colors upon thermal reactions with the color-forming substances 2a, 2b, and 2c to make up a multi-color recording material. When the layers 4a, 4b, and 4c are exposed to infrared rays lambdaa, lambdab, and lambdac corresponding to the absorbers 3a, 3b, and 3c respectively and heated, the substances 2a, 2b, and 2c are melted and reacted with the developers 5a and 5b in the layers 6a and 6b touched by the layers 4a, 4b, and 4c to cause chromogenic reactions, forming colored portions 7a, 7b, and 7c.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a recording medium that converts infrared energy into heat mode to form a colored image, and more specifically, it relates to a recording medium that converts infrared energy into heat mode to form a colored image, and more specifically, it relates to a recording medium that uses a plurality of light sources with different wavelengths of infrared light. The present invention relates to a multicolor recording medium that forms a multicolor image.

<Prior Art> Conventionally, thermal recording materials have been widely used in which a colored image is obtained by causing a contact reaction between a coloring agent and a coloring agent that reacts with the coloring agent to cause the coloring agent to develop color by heating. Generally, a thermal head having a heat generating element is brought into close contact with the recording layer of the recording body to heat the recording body to obtain a recorded image. However, problems with this method include abrasion of the thermal head, adhesion of debris on the head surface, adhesion between the head and the recording layer, and the limitations of high-speed recording because the recording speed depends on the heat dissipation time of the head. Examples include poor image resolution due to diffusion. As one means to improve these problems, it has been proposed to perform high-speed recording in a non-contact manner using a laser beam with high energy density.

On the other hand, there is an increasing demand for multicolor recording, and a large number of multicolor thermal recording systems have been proposed. As a representative example,
There is a multicolor thermosensitive recording material that has multiple laminated layers containing coloring agents and coloring agents with different coloring temperatures, but when the high temperature coloring layer develops color, the low temperature coloring layer must also develop color, and heating by thermal diffusion is required. Since the area around the part will also develop color, mixing the two colors,
There is a problem that color bleeding occurs and clear colored images cannot be obtained.

<Problems to be Solved by the Invention> The present invention was made in view of the above-mentioned problems, and its purpose is to use infrared rays to record multicolor images at high speed without mixing tones with each other. The object of the present invention is to provide a multicolor recording medium.

Means for Solving the Problems In order to achieve the above object, as a result of intensive studies, the present invention has developed an infrared absorbing material having a colorless or pale color forming substance at room temperature and an infrared absorbing material having a maximum absorption wavelength in the infrared region on a support. A plurality of layers containing a coloring agent and a layer containing a coloring agent that reacts with the coloring agent to form a color are laminated alternately, and the coloring material in each layer is a substance that develops a different color, and in each layer The present invention has led to the completion of a multicolor recording material characterized in that each of the infrared absorbers is a substance having a respective maximum absorption wavelength.

In the present invention, color-forming substances that produce different colors and infrared absorbers having different maximum absorption wavelengths coexist in the same layer, and a layer containing a color-forming agent that develops color by reacting with these color-forming substances under heat. The feature is that the layers are alternately stacked. With this structure, when the color-forming substance absorbs infrared rays, melts, and reacts with the color-forming agent in the adjacent layer to develop color, this color-forming agent-containing layer also serves as a heat diffusion prevention layer. , color mixing does not occur because other color-forming substances do not develop color.

The present invention will be explained in more detail with reference to the drawings. FIG. 1 shows color-forming substances 2a, 2b, 2 that develop different colors on a support l.
Infrared absorber 3a having a maximum absorption wavelength different from c
, 3b, 3c, and coloring agents 5a, 5b that react with these coloring substances when heated to develop color.
The structure of the multicolor recording medium of the present invention is shown in which layers 6a16b containing the following are alternately laminated. Infrared rays λa1λ corresponding to infrared absorbers 3as3bs3c in layers 4as 4bs 4c, respectively
b1λC is exposed to light and 3as3b, 3c are heated, and the heat produces color-forming substances 2a, 2b.

2c is melted and reacts with the coloring agents 5a and 5b in the layers 6a and 6b in contact with the respective layers to develop color, thereby forming coloring parts 7as7b and 7.
form c. In FIG. 1, a common coloring agent 5a is used for the coloring substance 2as2b, and a different coloring agent 5b is used for the coloring substance 2C, but in the present invention, each coloring substance and coloring agent The combinations may be the same or different. Furthermore, in the present invention, a two-color recording medium having the structure shown in FIG. 2 may be used, or a multilayer structure including these layers may be used.

In the present invention, the combination of a color-forming substance that is colorless or light-colored at room temperature and a coloring agent is not particularly limited, and any combination that causes a coloring reaction when the two come into contact with each other when heated can be used. Yes 1. For example, a combination of an organic acid metal salt and a reducing agent known as the 3M type used in ordinary thermal recording paper, a combination of a leuco dye and an acidic substance called NCR, and a combination of a diazonium salt and a coupler are used. I can do it. Among these, the NCR type is superior in terms of recording quality. As a material component of this NCR type, specifically, as a leuco dye, 3,6
-Dinithoxyfluorane, 3-dimethylamino-6-medoxyfluorane, 3-diethylamino-5-methyl-
7-chlorofluorane, 3', 6'-bis(diethylamino)spiro(phtala-cy) 1,9'-xanthine, 1,1-bis(p-aminophenyl)-phthalane, N-phenylleucoolamine, benzoyl Leucomethylene blue, crystal violet lactone, 3
-indolino-3-o-dimethylaminophenyl-6-
Dimethylaminophthalide, 3-diethylamino-7-chlorofluorane, 3-diethylamino-5-methyl-7
-t-butylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-
6-Methyl-1=o-butylanilinofluorane, 3-
diethylamino-7-dibenzylaminofluorane, 3
-cyclohexylamino-6-chlorofluorane, 3-
Diethylamino-6-methyl-7-xylidinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-7-cyclohexylaminofluorane, 3-biperidino-6-methyl-7-toluidi Nofluorane, 3-pyrrolidino-6-methyl-7-(p-
toluidino)fluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-N-methylcyclohexylamino-6-methyl-7-anilinofluorane, 3
-diethylamino-7-(m-trifluoromethylanilino)fluorane, 1,3-(N-,1-thyl-N-ynamylamino)-6-methyl-7-anilinofluorane, etc. However, it is not limited to these.

In addition, examples of acidic substances that develop color by reacting with the leuco dye include 4-phenylphenol, 4-1-butylphenol,
4-Hydroxyacetophenone, α-naphthol, B-
Naphthol, 2,2'-dihydroxydiphenyl, 2.
2'-methylenebis(4-chlorophenol), 2.
2'-methylenebis(4-methyl-6-t-butylphenol), methyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, 4,4'-isopropylidenebis(2-methylphenol), 4.4'
-ethylenebis(2-methylphenol>, 1.1'
-bis(4-hydroxyphenyl)-cyclohexane,
4.4'-isopropylidenediphenol, 4.4'-
Examples include, but are not limited to, cyclohexylidene bis(2-isopropylphenol), novolac type phenolic resin, 3.5-di-α-methylhensylsalicylic acid, and 4-hydroxybenzoic acid esters. .

Further, specific examples of infrared absorbers suitable for the present invention include I,
1'-diethyl-6,6'-cyclorho-4,4'-kitlicarposianine iodide, 1,1'-diethyl-4,4'-kitlicarposianine iodide, bis(
organic compounds such as nickel-tetrabutylammonium, furfuryl acetate, 2-ethylhexyldiphenyl phosphate, triphenyl phosphate, barium sulfate, calcium sulfate, barium carbonate, zinc carbonate, Sulfates, carbonates, nitrates, phosphates, silicates such as calcium nitrate, zinc phosphate, magnesium silicate, zinc silicate, nitrates such as boron nitride, silica mineral group, pyroxene group, silica group, hydroxide Examples include, but are not limited to, inorganic compounds such as metal hydroxides such as magnesium and metal oxides such as aluminum oxide.

In addition to the basic components described above in the present invention, inorganic and organic pigments such as aluminum hydroxide, heavy and light calcium carbonate, titanium oxide, barium sulfate, silica gel, activated clay, talc, clay, satin white, Kaolinite, polyolefin particles, polystyrene particles, urea-formalin resin particles, etc., and sensitizers such as stearamide, palmitamide, oleic acid amide, lauric acid amide, ethylene bisstearamide, paraffin wax, Furthermore, higher alcohols and higher resin acids may be added.

Furthermore, in the present invention, image stability is improved by adding benzophenone-based and benzotriazole-based ultraviolet absorbers, antioxidants such as hindered phenol and hindered amine compounds, and energy quenchers such as transition metal chelate compounds. is also possible.

A binder for forming a multicolor recording layer of the invention on a support such as paper, synthetic paper, resin film, or a composite thereof using the various components of the invention, and the multicolor recording. As a film forming agent for forming a film layer on the body, water-soluble or water-insoluble resin binders can be used, or water-soluble resins are preferably used, such as casein, gelatin, styrene-maleic anhydride resin, polyvinyl Alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, starch, isobutylene-maleic anhydride resin, diisobutylene-maleic anhydride resin, polyacrylamide, modified polyacrylamide, methyl vinyl ether, maleic acid copolymer, carboxymethyl cellulose, methyl cellulose, hydroxy Ethyl cellulose, hydroxypropyl cellulose, and as a water-soluble emulsion, vinyl acetate, polystyrene, acrylic ester, vinyl chloride-vinyl acetate copolymer, styrene-butadiene-acrylic ester copolymer, etc. are used alone or in combination. Furthermore, if necessary, a curing agent may be added to harden these binders to improve water resistance and chemical resistance.

In the multicolor recording material of the present invention, there are no particular limitations on the method of forming the color-forming substance-containing layer and the color-forming agent-containing layer, and conventional techniques such as air knife coater,
It can be applied to a support using a blade coater, bar coater, roll coater 1 printing, etc. and dried. or,
There are no particular limitations on the amount or thickness of these layers.

As the recording infrared ray of the present invention, a laser beam can be appropriately selected from infrared lasers such as a wavelength variable carbon dioxide laser, a carbon oxide gas laser, a YAG laser, and a semiconductor laser.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist of the present invention is exceeded. Hereinafter, parts represent parts by weight, and PVA liquid represents a 10% polyvinyl alcohol aqueous solution.

Solution A Solution B Solution C Solution Each solution was prepared by grinding and dispersing the mixtures of the above formulations in a ball mill for one day.

Example 1 50g of PVA in 100g of each of dispersions A, D, and B
The amount of coating after drying the added liquid is 2.5.2g each.
The mixture was sequentially coated on high-quality paper so as to have a color of /- and dried to obtain a two-color recording medium comprising a layer containing a black color-forming substance, a layer containing a coloring agent, and a layer containing a red color-forming substance.

When this two-color recording material was irradiated and recorded using a carbon dioxide laser with an infrared wavelength of 10.6μ under conditions of an output of 0.8W and 1.0m/s, a black colored image was obtained. When recording was performed by irradiating and recording 1.06 uI11 infrared rays at the same scanning speed using a YAG laser with an output of 0.8 W, a red colored image was obtained. No color mixture was observed in the black and red colored parts.

Example 2 A two-color recording material was obtained in the same manner as in Example 1 except that the B liquid in Example 1 was replaced with C liquid. Similarly, under the same conditions, the wavelength of this carbon dioxide gas laser was set to 1O16μ-, and then recording was performed with the wavelength changed to 9.2 urn, and a black and blue colored image with no color mixture was obtained.

Example 3 A paint mixture of DilOOg and 50 g of PVA liquid was applied to the two-color recording material obtained in Example 1 at a dry coating amount of 5 g/nt. After drying, 100 g of C liquid and 50 g of PVA liquid were applied.
A two-color recording material was obtained by applying and drying the mixed paint at the same concentration of <2 g/J.

When irradiated and recorded under the same conditions as in Example 1 with lO, 6u+++ and 9.2μ- carbon dioxide laser light, and 1.06gm YAG laser light, black, red, and black with no color mixture were obtained.
A blue colored image was obtained.

<Effects of the Invention> The multicolor recording medium of the present invention has a structure in which a layer containing a color-forming substance and an infrared absorber and a layer containing a coloring agent for the color-forming substance are laminated adjacently. , it is possible to obtain multicolor recording without color mixture by using a plurality of different infrared rays.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of a three-color recording medium showing an embodiment of the multi-color recording medium of the present invention, and FIG. 2 is a schematic cross-sectional view showing a configuration example of a two-color recording medium according to the present invention. . ■・・・・・・・・・・・・・・・Supports 2a, 2b,
3c...Color-forming substances 3a, 3b, 3c, each of which develops a different color...Infrared absorbers 4a, 4b, 4c, each having a different maximum absorption wavelength...Color-forming substance and infrared absorber-containing layer 5a, 5b...Coloring agent that reacts with different coloring substances to produce color

Claims (1)

[Claims] A layer containing a color-forming substance that is colorless or light-colored at room temperature, an infrared absorber having a maximum absorption wavelength in the infrared region, and a layer containing a color-forming agent that reacts with the color-forming substance to form a color are formed on a support. A multicolor recording material formed by alternately laminating a plurality of layers, wherein the color-forming substance in each layer is a substance that develops a different color, and the infrared absorber in each layer is a substance having a different maximum absorption wavelength. .