JPS6163838A - Reversible recording material - Google Patents

Abstract

PURPOSE:To make possible reversibly writing by light and heat by forming a recording layer consisting of a spiro-pyran compd. and binder on a base material. CONSTITUTION:The recording layer consisting of the spiro-pyran compd. expressed by the formula and binder is formed on the base material. Such recording material forms a color when UV rays from a light source consisting of a fluorescent lamp, etc. are irradiated thereto. The material can be decolored when said material is heated to about 100 deg.C by using a heat source such as heat roll or when visible light is irradiated thereto by using a light source such as xenon. The coloration and decoloration can be repeated by repeating the above-mentioned operation. A positive image is thereup obtd. by irradiating UV rays through, for example, a mask, onto said recording material and a negative image is obtd. by irradiating preliminarily the UV rays thereto to make the material form the color over the entire surface then imposing a transparent original thereon and heating the material by a heat sensitive head, etc. The good contrast and large coloration density are obtd. and since the fixability of the colored and decolored state is good, the material is usable as a repeatedly usable film for an OHP or heat-sensitive recording paper.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to reversible recording materials.

More specifically, it relates to reversible recording materials such as various recording and storage materials, copying materials, printing photoreceptors, photosensitive materials for lasers, photosensitive materials for phototypesetting, optical filters, masking materials, photometers, and display materials. It is something.

[Prior art]

It is known that spiropyran compounds have photochromic properties that cause color to develop or disappear upon irradiation with light, and various photochromic recording materials using the same have been proposed.

For example, in JP-A-Shojj-/4t9J'/, No. 2.

A photoclock recording material is described in which a spiropyran compound represented by the following general formula CAI is dispersed in a nitrocellulose resin. represents an alkyl group, R6 represents a hydrogen atom or an alkoxy group) Also, JP-A-Sho! θ-λ♂/λda publication KFi describes a photochromic recording material in which a spiropyran compound represented by the following general formula [B] is dispersed in a polymeric compound having an alcoholic hydroxyl group. Ro is a hydrogen atom, ) is a Rodan atom.

Photochromic recording materials are usually used by forming a film in which a polymerized spiropyran compound is dispersed as described above. For recording materials consisting of a combination of inders.

Since mutual compatibility and solubility are not necessarily sufficient,
It is not possible to increase the concentration of the spiropyran compound, and as a result, a recording material with good contrast and rapid color development fMk cannot be obtained. Furthermore, in the prior art, 1
The fixing properties of the colored and decolored states are not necessarily sufficient.

Since recorded images could not be stably obtained, there were problems such as the inability to use the method repeatedly.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a recording material that is reversibly writable by light and heat using a new spiropyran compound. [Structure of the Invention] The present invention provides the following general formula (1)% formula%) (wherein n represents an integer of / to It has a recording layer consisting of a spiropyran compound represented by Φ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R3 represents an alkyl group, and a binder. The gist of the material is a reversible recording material characterized by Examples of the alkyl group of 'IMI include h'1 to 6 alkoxy groups.Also, examples of the alkoxycarbonyl group represented by R1 include:
The alkoxycarbonyl group of 01 to 6 is single. and.

The alkyl group represented by Hs is C8-2. The spiropyran compound of the present invention, which includes an alkyl group, can be produced, for example, as follows.

That is, −13°3 is expressed by the following general formula []] (wherein II is the same as the above-mentioned definition)
-Trimethylindolenine visiting conductor VC, the following general formula (I
) (wherein R3 and n are the same as defined above)
) Luenesulfonic acid esters can be produced by reaction step 1 and then a nitrosalicylaldehyde preconductor represented by the following general formula [IV] (where RtFi is the same as defined above).

The alkylation reaction involving p-toluenesulfonic acid ester represented by the general formula [JU] is carried out by hot melting sbrut, -,
The reaction can be carried out in a nonpolar solvent such as an aromatic solvent such as chlorobenzene or dichlorobenzene at a reaction temperature of ♂O to aOO°C.

Preferably, it can be smoothed without a solvent at 130 to 110°C.

In addition, the reaction with the nitrosalicylaldehyde derivative represented by the general formula (IVI) can be carried out in the presence of a basic catalyst such as piperidine, piperazine, or morpholine, using an alcoholic solvent such as methanol, ethanol, propatool, or butanol, It can be carried out in the presence of a tough or non-uniform solvent such as a ketone solvent such as acetone or methyl ethyl ketone, or a halogenated hydrocarbon solvent such as dichloromethane or trichloroethane.

The reaction temperature can be smoothly carried out at 4 to 20°C in the presence of a piperidine catalyst in acetone at a temperature of 0 to 100°C.

The binder used in the Kffi of the present invention may be any binder that is compatible with spiropyran and has excellent film-forming ability, such as polyester resin, polycarbonate resin, polymethyl methacrylate resin, polystyrene cuff,
Polyvinylidene acetate resin, polyacetated vinyl resin, polyvinyl butyl-poor resin, cellulose acetate resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer.

Examples include polypropylene resin, polyethylene resin, polyacrylonitrile resin, urethane resin, and epoxy resin. Particularly preferred are polyester resin and polycarbonate resin.

What is the content of spiropyran compound in the FyII/c of the present invention?

For the binder, it is effective to use 0.1 to 100% (by weight), but for the recording material, it depends on the film thickness.

The above 1@I21! is related to the type of base material, etc. I/c
It is not something that can be determined.

The recording material of the present invention can be produced by the following method. First, a spiropyran compound represented by the general formula [■] and a binder.

Dissolve in a common solvent to produce ink.

Then, by applying the obtained ink onto a suitable base material and drying it, the recording material of the present invention can be produced.The solvent used in producing the above-mentioned ink is as follows.

Ketone solvents such as methyl ethyl ketone, acetone, and tetrahydrofuran, xylene, and benzene.

Benzene-based solvent such as toluene 1. Ethyl acetate.

Examples include ester solvents such as butyl acetate.

Moreover, these solvents can be used alone or as a mixed solvent.

In addition, examples of the base material for manufacturing the recording material include polyester, polyimide, polycarbonate, ;11+) methyl methacrylate, glass, and metal-free paper.

The recording material of the present invention is a fluorescent lamp or a high-pressure mercury lamp.

Coloring can be achieved by irradiating ultraviolet light from a germicidal lamp or other light source, and a heat-sensitive head.

Discoloration can be achieved by heating at a temperature of around 100°F using a heat source such as a heat roll, or by irradiating visible light using a light source such as xenon, and repeating this operation. I'm busy with all the things I need to do, so I'm going to colorize and erase the color.
Further, the recording method using the recording material of the present invention includes a recording method in which a transparent original or mask is placed on the recording material and a positive image is obtained by irradiating the recording material with ultraviolet rays; After irradiating the entire surface with UV rays in advance to develop color, there are recording methods such as placing a transparent original on top and irradiating it with strong visible light or visible laser light such as an Ar+ laser, or heating it with a thermal head to obtain a negative image. Can be mentioned.

〔Effect of the invention〕

The recording material of the present invention has good contrast and high color density, and also has good fixing properties in single color and decolorized states, so it is possible to obtain an OHP film or heat-sensitive recording paper that can be used repeatedly.

Example/ J, j, j-)limethylindolenine represented by the following structural formula/
J-09? and p-)luenesulfonic acid methoxyethoxyethyl ester represented by the following structural formula, 26. A mixture of At 3 at 74tθ℃
After reacting for an hour, cool to room temperature and add 4tO of ethanol.
Adding O-, nitrosalicyl altehyde represented by the following structural formula/7. .

2 and piperidine ion under reflux.

The reaction mixture was stirred for 7 hours, extracted with ether/l, cooled, and treated with P. The solvent was distilled off from the P solution to obtain a crude product j7. Of was obtained and then recrystallized using ethanol to obtain a spiropyran compound (melting point: ~93°C, colorless crystals) represented by the following structural formula. The mass spectrum showed M/e-4t10.

C,H,QC,I(,OCH.

Using the nine spiropyran compounds obtained in this way,
An ink having the following composition was prepared.

The above spiropyran compound 0. ♂t polyester resin 3. jf (Byron-〇〇,
Manufactured by Toyobo Co., Ltd., Mai Ni Co., Ltd., product name) Methyl Ethyl Ketone 209th Iterber Coater (RK Pr
A polyester film (manufactured by Diafoil Co., Ltd., thickness io.

μ) KThe above ink was applied and dried at 70°C for 2θ minutes, and the film thickness was 3μ.
-PRI NTKR/lrOVO)
If it is carried out for seconds, it becomes a highly concentrated blue-violet color (λmaw = 670 n
m) developed color. The colored material adhered to the feet very well. Next.

Heat roll (manufactured by Canon Co., Ltd., KAL-DK-V
F! LOPKRJtOH) Te/ / When heated to 0°C, it returned to its original colorless state. I was able to repeat this change.

Example The following procedure was carried out according to the method of Example, except that p-toluenesulfonic acid methoxyethyl ester 23.02 was used in place of p-)toluenesulfonic acid methoxyethoxyethyl ester 26.29. A spiropyran compound (melting point: /7- to /7g°C) represented by the structural formula was obtained.

0,H,0OH8 The above-mentioned spiropilay compound 0. An ink having the following composition was prepared using this compound. ♂2 Polyester resin -1 of (Byron 10
3. Manufactured by Toyobo Co., Ltd., black market name) Methyl ethyl ketone −〇? The ink having the above composition was applied according to the method in Example/, and after drying, a polyester film (recording material) having a recording layer with a film thickness of μ μ was obtained.
When you perform
m) developed color. The consistency of the colored product was good.

Next, a thermal head was used in which a polyimide film (thickness !μ) was superimposed on the recording Mt (l!I) of the recording material, and one heating resistor was provided at a density of 1/2.

o, tw Apply heat for 10 milliseconds with 7 dots of power.

When thermal recording 6 was carried out, the heated portion returned to its original colorless state and negative recording was possible.This change could be reversed.

Actual/Ai Example 3 A compound represented by the following structural formula % formula % (), 2. L7? ethanol 100-
After dissolving in the solution, a compound represented by the following structural formula / 4,7t was added, and the mixture was refluxed.

The mixture was stirred for several hours to carry out two reactions. Then cool to room temperature,
The precipitated crystals were filtered, washed, and air-dried to form a spiropyran compound represented by the following structural formula (melting point d' J- to d' 4°C).
, colorless crystal B) 3'p,ot was obtained.

C7H40Ce”+5(n) Using this compound, an ink having the following composition was prepared.

The above spiropyran compound 0. ? ? Polycarbonate resin 2.01 Chloroform
Gu0? Coloring and erasing can be carried out by applying an ink having the above composition according to the method in Examples, and after drying, heating the recording layer with a film thickness of μ with a roll. The color fixability was good.

EXAMPLES According to the method of Examples/--3, a number of spiropyran compounds shown in Table 1 below were weighed, mixed together with a polynistenol resin, and prepared in a vacuum. Then, the obtained ink was applied to a polyester film with a color tone and λm
The fixability of the colored material developed on aX was good. It was then heated with a heat roll or a heat sensitive head to return to its original colorless state. This change could be repeated.

Claims (1)

[Claims] (1) On the base material, there is the following general formula [I] ▲Mathematical formula, chemical formula, table, etc.▼‥‥‥‥‥[I] atom,
halogen atom, alkyl group, alkoxy group or alkoxycarbonyl group, R^2 represents a hydrogen atom, halogen atom, alkyl group or alkoxy group, R^3 represents an alkyl group) and a binder. A reversible recording material characterized by having a recording layer consisting of.