JPS59143681A - Manufacture of development sheet for image recording - Google Patents

Abstract

PURPOSE:To obtain a development sheet having a high smoothness, a high lustrousness and excellent printability by a method in which a plastic paint film containing an electron acceptor substance is pressingly contacted with the surface of a metal drum of a high lustrousness for nonplastic mirror finishing. CONSTITUTION:In the case of a thermal coagulation method, for example, a coating liquid 2 containing an electron acceptor substance is coated on a high- quality paper 1 by an air blade 3, and the wet paint coat film surface 4 immediately after being coated is heated by an infrared heater 5. The paint film is pressed on the surface 6 of a rotary chromium-plated drum heated by a rubber roll 7, dried, and separated to obtain a development sheet having a high smoothness and a high mirror surface lustrousness, and capable of coloration with an electron-donative colorless dye. The electron acceptor substance used is preferably inorganic solid acids such as activated clay, etc., from the standpoints of cast characteristics, heat resistance and chromogenic property. As the electron- donative colorless dye, triphenylmethane-based latone dyes, spiropyrane type dyes, etc., are used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an image recording material such as a pressure-sensitive recording paper, a transfer-type heat-sensitive recording paper, etc., which is composed of a complete combination of an electron-donating colorless dye and an electron-accepting substance. The present invention relates to a method for manufacturing a novel color developing sheet.

The most famous image recording material that utilizes the color-forming reaction between an electron-donating colorless dye and an electron-accepting substance is pressure-sensitive copying paper that uses microcapsule technology to fully utilize oil microcapsules in which the electron-donating colorless dye is completely dissolved. and has already been widely commercialized.

This pressure-sensitive copying paper appears to be colorless paper, but it is possible to obtain a plurality of colored recordings. This pressure-sensitive copying paper does not stain hands or clothes unlike conventionally used carbon paper, and has come to be widely used for slips. Furthermore, with the improvement of office efficiency, labor saving, and the spread of computers, the use of N1 for various purposes has been promoted, and the growth in n1 has been remarkable in recent years.

Pressure-sensitive copying paper consists of a sheet coated with microcapsules of microscopic oil droplets of a hydrophobic non-volatile solvent in which an electron-donating colorless dye is completely dissolved, and a color developer sheet coated with a water-based paint containing all electron-accepting substances. The microcapsules are destroyed by the printing pressure of various types of printers, etc., and the spilled electron-donating colorless dye liquid contacts the electron-accepting substance, causing a chemical reaction and coloring. Records are what you get.

On the other hand, in the heat-sensitive recording method, a donor sheet prepared by coating or impregnating a deuteron-donating colorless dye on a support with good thermal conductivity together with all the wax, a color developer sheet coated with an electron-accepting substance, and a color developer sheet coated with an electron-accepting substance, They are placed facing each other, and thermal printing is performed using a thermal head from a fly on a good heat conductive support.The electron-donating colorless dye wax is melt-transferred to a color developing sheet fully coated with a single-electron-accepting substance, and the reaction is carried out. A system that develops color and records images.

In addition, in recent years, a donor sheet prepared by coating or impregnating a thermally conductive support with a colorless sublimation dye as an electron-donating colorless dye and a color developing sheet fully coated with an electron-accepting substance have been developed. A method has been studied in which the two sides are placed facing each other and additional printing is performed using a thermal head or the like, and a colorless sublimable dye is completely sublimated to obtain an image on a color developing sheet.

In the heat-sensitive recording method of 几 et al.
(:';n) A color image can be easily obtained by creating an image and performing eight printing steps corresponding to the original on the same color developer sheet.

The present invention relates to a method for manufacturing a novel blood-colored sheet for image recording used in these pressure-sensitive and heat-sensitive recording systems. If necessary, the coating liquid may contain inorganic pigments such as kaolin, clay, carbonaceous, starch, water-soluble polymers such as PVA, adhesives such as synthetic resin emulsions, surfactants, antifoaming agents, wax, etc. additive? In addition, the coating was applied to a support such as paper using a coater head such as an air knife, a rubber doctor, a golade, or a roll and dried, and the coating was smoothed through the nip of a machine calender, a supercalender, etc.

These color developing sheets have no problems when used for ordinary slips, but they are suitable for applications that require high smoothness and high gloss.
In addition, in order to obtain higher quality images, especially color images using a thermal method, high smoothness is required from the viewpoint of adhesion with the electron-donating colorless dye sheet and adhesion with the thermal head. High gloss was required for contrast and image sharpness, and conventional sheets were insufficient.

As a result of intensive studies, the inventor of the present invention applied all methods of cast-coated paper, which has high smoothness and strong gloss as a high-grade printing paper, to apply a coating layer containing an electron-receptive substance to a gold-plated drum surface with a high gloss surface. By pressing the entire coating layer in a plastic state and applying a non-smooth surface finish, when used as pressure-sensitive recording paper, you can obtain printing with a highly smooth surface, strong gloss, and good contrast.
In addition, a color developer sheet with excellent printability can be obtained, and when used in the heat-sensitive color developer sheet described above, the surface has a high smoothness and image quality with good gradation in strong light R, especially high quality. A color image? It has been found that excellent materials can be obtained, leading to the present invention.

The receptivity of the present invention is good (the entire surface of the chromium-containing Cr coating layer is good!).
As for the method of performing the dual casting finish, simply add pigments, adhesives, mold release agents, and other additives to the liquid containing the electron-receptive substance.
After applying all of the water-based paint added, drying and peeling the I-E while it is still attached to the heated metal solid surface will reduce the effect.
In that case, unless the solid metal surface is below 100°C, the coating solution will boil and the coating layer will be destroyed, and a homogeneous cast surface cannot be obtained, so the temperature has to be lowered completely. The ship is very slow and has a 5 poor productivity rating.

As an improvement method, as described in Japanese Patent Publication No. 88-15751, Japanese Patent Publication No. 5888-1988, Japanese Patent Publication No. 88006-1988, Japanese Patent Publication No. 4g-88882, etc., a wet coating is applied to the base paper. A method in which the surface of the layer is brought into contact with an aqueous solution containing a coagulant such as an acid or salt, the coated layer is completely coagulated, and then pressed onto a solid metal surface and dried.
The entire coating layer is heated as a solid coagulated layer by adding the entire delyte and heating it to make it a thermocoagulable coating liquid, and then heating it to a pseudo-solid temperature of 1 F or higher to completely solidify the protein adhesive. There are methods such as pressing and drying the metal drum surface, and methods 2 and 4 can also be applied to the present invention.

Examples of electron-accepting substances in the invention include activated clays, phenols (Hibun@4n-9B 09, Special Publication No. 4
2-8257), oil-soluble acidic phenol polymers (Japanese Patent Publication No. 42-20144), burnt modified products of phenol polymers (Japanese Patent Publication No. 55-25998), Kakki carboxylic acid derivatives (Japanese Patent Publication No. 49-10856, Tokuko Sho 55-2699
No. 8) etc. have been put into practical use, but the invention is not necessarily limited to these. However, in terms of casting properties, heat resistance and coloring properties, inorganic solid materials such as activated clay are more preferred.

Therefore, the inorganic solid acid is 810.degree. The resulting clay mineral is contacted in an aqueous medium with compounds of magnesium and/or aluminum that are at least partially soluble in the medium, such that the soluble compounds are dissolved in water. In the case of substances other than oxides, it is neutralized with an alkali or acid to reduce the formation of hydroxides, and all magnesium and/or aluminum components are introduced into the nucleic acid-treated clay ore's proboscis, and if desired, by drying. Of course, it is also good for manufacturing or semi-autogenous solid coughs.

A beautiful color developing sheet with a strong light finish as in the present invention is not yet known, and other known methods require a super calender finish to improve surface smoothness and gloss. Although it is normal, it is impossible to obtain a high-light ceiling surface like that of the present invention. Strong gloss developing sheet of the present invention?
For the first time, it became possible to obtain truly beautiful strokes.

For example, the color images obtained by the above-mentioned heat-sensitive method, particularly the colorless sublimation dye coloring method, are glossy and beautiful and are comparable to color image prints made by the silver salt photographic method.

The greatest feature and effect of the present invention is that not only the white portion (non-printing portion) but also the colored portion (printing portion) exhibits strong gloss to provide a beautiful image.

As the uninvented deuteron-donating colorless dye, a8-bis(
p-dimethylaminophenyl)-6-dimethylaminophthalide, a8-bis(p-dimethylaminophenyl)-
↓56 Triphenylmethane-based lactone dyes represented by futetrachlorophthalide, etc.

Fluorane-type dyes represented by 8-diethylamino-6-methyl-di-anilinofluorane, 8-diethylamine-6-methyl-7-chlorofluorane, etc., acylated leucothiazine-type dyes, and acylated leucothiazine-type dyes. Dyes, lactam dyes, spiropyran dyes, etc. can be used.

In addition, as colorless sublimable dyes, heptanazine compounds described in JP-A No. 52-5527, indole compounds, his-(
44'-dimethylaminophenyl), 44I~
bis-(di-lower alkylamino)-diphenylmethane,
2-substituted vinylene-a8-dimethyl-8H-indole, 44'-bis-diphenylmethane derivatives described in JP-A-52-20884, N-bis-(4-dialkylaminophenyl)- as described in JP-A-52-208B5 Methyl-β-hydroxyethylani! J 7,'% Kaisho 52-
Michler's ketone described in No. 24580, JP-A-52-24
N-bis-(P-dimethylaminophenyl)-methyl-m-hydroxyethylaniline described in No. 581, pyridine-carbo/acid lactam described in JP-A No. 52-55585, lactam of pyridine-carbo/acid described in JP-A No. 52-88027 a6-dialkoxy-fluorane, a6-sialkoxyfluorananilide, indolinobenzospirobilane described in JP-A-52-158440, N-(indol-8-yl) described in JP-A-58-81188 Methylideneamine derivatives, acylleucophenooxazines described in JP-A No. 58-42788, spirobenzopyran indoles described in JP-A-54-28140, JP-A-54-1405111
Schiff base compounds described in No. 9 and the like can be used, but are not necessarily limited thereto.

In addition, electron-accepting substances such as Kanakuramu lacquer (II) include four-child donating colorless dyes as extender pigments within the range that does not completely inhibit color development, clay minerals such as kaolin, clay, and charcoal, and adhesives such as protein-based Adhesives, starch adhesives, other water-soluble polymer adhesives, and synthetic resin emulsion adhesives can be used alone or in combination.

In addition, mold release agents such as stearin soda, ammonium stearate, paraffin, potassium oleate, octanol,
Additives such as antifoaming agents such as tributyl phosphate and viscosity 11 reducing agents such as dicyandiamide can be used as necessary.

Next, in order to explain the present invention more specifically, all examples will be given.

Example-L I liquid ■Liquid Bustyrene nokjie 2 joint emulsion l
O modified appetizer capital (Asahi DOW DOW Latex512R50%
Water) Solid liquid calcium chloride L8 parts by weight Water I LTIV liquid ammonium stearate α8 parts by weight Water
2.7 11-M・■・Plate・V
With the equipment shown in Figure 1, as a coating liquid with a total concentration of 40%,
Coating liquid 2 20% due to drying conditions on high-quality paper 1 with a total of 8697 nt
Apply with an air blade 8 to a thickness of 177 m', and immediately after coating, heat the wet coating surface 4 with an infrared heater 5 to a temperature of 50°C or higher, and f'L'518Q°C.
It was pressed onto the heated rotating chromium plating drum surface 6 with a rubber roll 7 and peeled off after drying to obtain a color developing sheet which had a highly smooth surface and mirror gloss and was capable of developing color with an electron-donating colorless dye.

This blood-colored sheet was placed facing the coated side of pressure-sensitive recording paper (Mitsubishi 808 paper blue), and the result was printed using a typewriter.
Compared to ordinary color developer sheets for pressure-sensitive recording paper, it has a good surface smoothness, strong gloss, and very good color contrast, and is excellent in printability.

In addition, this color developer sheet and stearinamide 10 parts by weight 5% hydroxyl 7 ethyl cellulose 50 l Crystal violet lactone 10 1 7 Grinded in a ball mill for 8 days and printed on glassine paper to a dry weight of 10 i/m" The coated surface of the smeared electron-donating colorless dye sheet was placed opposite to the coated surface, and printed using a thermal fax machine (Toshiba KB-50 [1) at a head voltage of 17 to 21 V. The result 1 was a highly smooth one with very good contrast. , I rarely found one with a strong luster.

In addition, this color developing sheet and N[4-(N-methyl-N-benzylamino)-benzilitine:]-4-methylanili/
.

4-(La8-)limethyl-indolino)methyl-7-
(N-methyl N-phenylamino-11゜flr g
+ ) Limethylsuviro(2H-1-penzoviranose 21- [2+H: l -indole].

a7-Bis-diethylamino-N-dichloroacetylphenoxazine (all of these 8 dyes are colorless sublimation dyes) were dissolved in 1% dichloromethane and impregnated with condenser paper, and the sheets were placed opposite each other to form a condenser. As a result of printing from the back of the paper with a thermal fax machine (Toshiba xB-soo) at a head voltage of 17V to 21V, the result is a sheet with high smoothness and high gloss compared to ordinary pressure-sensitive color sheets, with vivid gradation of contrast. Good yellow, magenta,
A beautiful color image with cyan as eight primary colors was obtained. Not only the white areas but also the colored areas (printed areas) are fully glossy.

Example-2 I liquid ■liquid ■liquid Styrene-butadiene copolymer kneer A/C*7
(Asahi DOW Latex 612B 48% moisture)
Combine 18 parts by weight of I, ■, ■ liquids, and add 1 part by weight from funnel oil
Add 4 parts and 1 part by weight of Octatool α to make the coating liquid 42% thick. Using the apparatus shown in Figure 2, apply coating liquid 2 to 80 g/m" high-quality paper so that the dry weight is 20.9/m'. Apply 1% 5% sand solution of 4 using air blade 8 and heat at 180℃.
A color developing sheet with a highly smooth surface and strong gloss is pressed onto a heated chrome-plated sheet with a rubber roll 5, pressed, dried and peeled off. All printing was performed in the same manner as in Example 1, and good results were obtained. In particular, the color images obtained by the heat-sensitive method were splendid, with not only the white parts but also the colored parts being glossy and vivid.

Example-a The same procedure as in Example-1 was carried out using the ① liquid tray, and the same good results were obtained.

[Brief explanation of the drawing]

FIG. 1 is a drawing showing the equipment used in the casting method using the thermocoagulation method. FIG. 2 shows an apparatus 1.1 for the salt or acid casting method. ! ...Base paper 2...Coating liquid (containing electron-accepting substance) 8-a@Airblade 4...Coating layer 6 immediately after Airflade coating 6...Infrared heater 6...Cast drum 7...・Rubber roll 8...Coagulation bath

Claims (1)

[Scope of claims] Method for producing a color developing sheet. (21) The method for producing a color developing sheet for image recording according to claim 1, wherein the electron-accepting substance is an inorganic solid acid.