JPS58215397A - Volatile coloring matter composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition capable of being used in a heat-sensitive recording sheet and also of forming a picture having excellent resolution on a printing paper by using a crosslinkable resin as a part or all of a binder to be included in the titled composition. CONSTITUTION:A coloring matter composition is obtained by dispersing 1- 20wt% an organic dye volatilizable from solid or liquid state at 100-200 deg.C, having a comparatively small molecular weight, and 2-40wt% a crosslinkable resin as a binder into a solvent, e.g., water, alcohols, esters, etc. The crosslinkable resin used includes ones consisting of a combination of a natural or synthetic resin having reactive functional groups and a crosslinking agent or a curing agent or of a radiation-curable and crosslinkable resin mixed with a photopolymerization initiator as needed. In this case, in order to obtain a properly crosslinked resin, the amount of the crosslinking agent, etc., is preferably adjusted and also a thermoplastic resin and a plasticizer are preferably added in an amount less than about 30wt% of the total amount of the binder used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vaporizable dye composition used in the preparation of heat-sensitive recording sheet materials for forming sharp images with excellent resolution on photographic paper.

2. Description of the Related Art Conventionally, systems have been developed for directly reproducing images taken with a video camera or still images from a television, VTR, video disc, computer, etc. in full color on photographic paper. The color-forming material used in this system is a dye that vaporizes when heated and dyes the photographic paper.It is usually provided on the surface of a sheet base material such as paper using a synthetic resin binder, and the sheet material is dyed onto the photographic paper. The dye is superimposed on the image and heated according to the image using a special thermal head to vaporize the dye.
It is transferred onto photographic paper. Although such vaporizable dye-coated sheet materials are known in the field of thermal transfer printing technology, such known 7-sheet materials cannot be used as sorting materials for thermal recording in the above-mentioned system. . One reason for this is that conventional thermal transfer printing methods use overlapping heating for a relatively long time (7,
The above-mentioned new system requires a relatively high temperature due to the extremely short heating time, and the material to be transferred is not woven fabric but a sheet material with a smooth surface (photographic paper), so the sheet material for thermal recording is photographic paper. This is because not only the dye but also the binder itself is transferred to the photographic paper, resulting in lower resolution, loss of image sharpness, and difficulty in achieving gradation.

As a result of intensive research aimed at solving the above-mentioned drawbacks, the present inventors succeeded in obtaining a vaporizable dye composition that provides a heat-sensitive recording sheet that overcomes the above-mentioned drawbacks of the prior art.

That is, the present invention is a vaporizable dye composition comprising a vaporizable dye, a binder, and a solvent, and a part or all of the binder is a crosslinkable resin.

To explain the present invention in detail, the volatile dye used in the present invention is a comparative example with a small molecular weight (for example, about 200
~400) It is an organic pigment, which is included in large amounts in conventionally known sublimable dyes and disperse dyes, and has a pigment content of approximately 100 to 200.
It vaporizes from solid or liquid at a temperature of °C (normal pressure) and dyes hydrophobic synthetic resin materials such as polyester, polypropylene, acetate, etc. In terms of chemical structure, it is azo-based and anthraquinone-based. The main dyes are styryl, quinophthalone, nitrodiphenylamide, etc.

One embodiment of the binder used in the present invention is composed of a natural or synthetic resin having a reactive functional group and a crosslinking agent or curing agent. .

The main reactive functional groups are hydroxyl group, 2°L box/l group, amino group, isone group, -to group, evoquino group, etc. Resin materials having hydroxyl group include cellulose derivatives, gum arabic, etc. , tiger cant gum, starch derivatives, alginic acid derivatives, polyvinyl alcohol,
There are polyvinyl alcohol derivatives, acrylic polyols, alkyd resins, etc. Those with carboxyl groups include alkyd resins, cellulose derivatives, and polymers or copolymers of unsaturated carboxylic acids, and those with amine groups include melamine. There are resins, urea resins, etc. Those with ynone groups include various polyynone anot compounds, terminal ynone abut prevolimers, etc., and those with epoxy groups include various epoxy resins. .

As a crosslinking agent or curing agent to be used in conjunction with the above resins, the above resins having a functional group that can react with the functional group of the resin selected from the resin materials mentioned above can be used as a crosslinking agent or curing agent as is, and various Norankanosoling agent, titanium coupling agent, zirconium chelating agent, aluminum chelating agent, Mg, Ca, Zn
, Pb and other polyvalent metal compounds, organic acids, inorganic acids, various inorganic and organic salts, metal soaps, various polyamines, and other conventionally known crosslinking agents or curing agents can be used.

Another example of a crosslinkable resin that can be used in the present invention is a resin that is cured and crosslinked with radiation such as ultraviolet rays or electron beams. Such resins are composed of monomers, prepolymers, polymers, or mixtures thereof having at least one polymerizable unsaturated double bond in their structure, and optionally contain a photopolymerization initiator. l. These crosslinkable resins themselves are known.

The binder in the present invention may be only a crosslinkable resin as described above, but if the binder is used alone, if crosslinking progresses too much later, vaporization of the dye contained therein may be hindered. It is preferable to appropriately adjust the amount of the agent or curing agent used, or to add a conventional thermoplastic resin or various suitable plasticizers to the crosslinkable resin of AI2 above to ensure smooth vaporization of the dye. . Such conventionally known thermoplastic resins include non-reactive cellulose derivatives, vinyl polymers, polyesters, and polyamides, and any conventionally known plasticizers may be used. When such a thermoplastic resin or N3 plasticizer is used, it should be used in an amount of about 30 weight φ or less based on the total amount of the binder. Above.

In addition to water, the solvents used in the present invention include alcohol, ester, keto), aromatic, aliphatic, naphthenic,
Various solvents such as inoparaffinic solvents can be used alone or in mixtures.

The basic ingredients of the composition of the present invention are as described above,
In addition, various conventionally known additives and fillers can be used as necessary.

The composition of the present invention is manufactured by blending the above-mentioned components and carrying out a normal dispersion treatment. A ratio of 2 to 40% by weight, such that the solvent is about 40 to 97% by weight, is preferred.

The dye composition of the present invention obtained as described above is a liquid composition, and can be coated with a blade coater, an air knife coater, a roll coater, a curtain coater, a bar coater, etc.
Approximately 01 to 2jj/+n is applied onto a sorted substrate, preferably thin paper, by a known coating means such as a gravure coater.
' (However, the amount of dye) is applied, cross-linked and cured by heating and drying or irradiation with radiation, and if necessary further heat-treated to provide a heat-sensitive recording/human material. By crosslinking the binder in the composition and forming a three-dimensional network of the resin in this way, the -/-to material is superimposed on the photographic paper and the vaporizable dye is transferred to the photographic paper using a thermal head in accordance with the video signal. Even if an image is formed by
This prevents excessive adhesion between the pigment sorting material and the photographic paper, which would cause the binder in the pigment layer to become excessively soft or sticky due to the heating of the thermal head, and also prevent the binder itself from transferring to the photographic paper. , it becomes possible to form a clear image.

According to the inventor's detailed research, the vaporization of the dye cannot be prevented;
It has been found that the most preferred example of a crosslinkable binder that does not cause excessive adhesion to the photographic paper is a mixture of cellulosic derivatives and melamine resins.

Especially when using radiation-curable resin as a binder,
Even though heating is required during the crosslinking and curing, the crosslinking and curing is completed in several seconds to several minutes, so there is no volatilization of the volatile dye, which is preferable from the viewpoint of productivity.

Next, the present invention will be specifically explained with reference to Examples.

Note that the terms ``department'' or ``section'' in the text are based on weight.

Example 1 5 parts of Kayaset Yellow AG (Nippon Kayaku), 3 parts of levoquinomethyl cellulose, and 3 parts of levoquinomethyl cellulose were dispersed in a polyvinyl alcohol ball mill, and further methylolmelamine (
A vaporizable dye composition of the present invention was obtained by adding 1 part of crosslinking agent) and 0.1 part of ammonium chloride.

Example 2 The vaporizable dye of the present invention was prepared using 10 fB of Kayana Trend B (Nippon Kayaku), cellulose acetate fluoride IS[, 2 parts of silica, 73 parts of toluene, and 3 parts of quinolile/duino/anate. A composition was obtained.

Example 3 The same procedure as in Example 2 was carried out, except that 1 part of tetrabe/diltite was used in place of the quinolenedi dino/anate of Example 2, and 150 parts of the solvent tositeluene and 23 parts of inopropyl alcohol were used. A vaporizable dye composition of the present invention was obtained.

Example 4 10 parts of PTB-67 (blue pigment, Mitsubishi Kasei), 15 parts of filtrate cellulose, 1 part of silica, and 74 parts of toluene were blended, and after dispersion treatment in a seven-tree mill, 2 parts of methylolmelamine and Paratonol were mixed. A vaporizable dye composition of the present invention was obtained by adding 0.5 part of ensulfonic acid.

Example 5 10 parts of Kayasent Blue 906 (Nippon Kayaku), 20 parts of epoxy resin, 30 parts of toluene, 38 parts of diacetic alcohol, and 2 parts of silica were blended and dispersed in an attritor. 5 parts of methylolmelamine and 2 parts of zoethyle/triamino were added to obtain the vaporizable pigment composition of the present invention.

Example 6 Kayasenoto Yellow AGIO part, 50 parts of polyester f acrylate, 5 parts of silica and 35 parts of l-noshiko were blended and dispersed in a sand mill to obtain a volatile pigment composition of the present invention.

Example 7 Kayaset Yellow B (Nippon Kayaku) 10 parts, trimethylolpropane triacrylate 60 parts, benozophenone 3
1 part, 3 parts of methyljetanolamine, 2 parts of silica, and 22 parts of xylene were blended and dispersed with an attritor to obtain a vaporizable dye composition of the present invention.

Example 8 PTB -6710 parts, polyester acrylate 20
parts, cellulose acetate propionate 10 parts, be/
A vaporizable dye composition of the present invention was obtained in the same manner as in Example 7 using 1 part of diyninobutyl ether, 19 parts of inopropyl alcohol, and 40 parts of Toluev.

Example of Use Using the compositions of the present invention in Examples 1 to 8, heat-sensitive recording materials were obtained under the conditions shown in Table 1.

Comparative Example 1 in Table 1 above is an example in which quinrylene diisocyanate was not used in Example 2, and Comparative Example 2 is an example in which methylolmelamine and p-toluenesulfonic acid were not used in Example 4. It is.

Patent applicant: Noni Co., Ltd. Same Dainichiseika Kagyo Co., Ltd. Agent: Patent Attorney Souo Suga

Claims (3)

[Claims] (1) A vaporizable dye composition consisting of a vaporizable dye, a binder, and a solvent, in which part or all of the binder is a crosslinkable resin. (2) The composition according to claim (1), wherein the crosslinkable resin comprises a natural or synthetic resin having a reactive functional group and a crosslinking agent or a curing agent. (3) The composition according to claim (1), wherein the crosslinkable resin is a radiation-curable resin.