JPS58179693A - Recording method - Google Patents

Abstract

PURPOSE:To obtain stable recording by a method in which a recording medium provided with a layer containing a diazonium perchlorate and a colorant of a specifically max. absorption wave length is subjected to the irradiation of lasers of a wave length close to that of the colorant and then to the irradiation of ultraviolet rays to inactivate chromogenic reagents remaining after recording. CONSTITUTION:A recording medium, formed by providing a layer containing a diazonium perchlorate (e.g., p-diazo-N,N-dimethylaniline perchlorate, etc.) and a colorant (e.g., brilliant green, etc.) having a maxiumum absorption wave length of 450nm or more as absorption characteristic on a base material (e.g., glass plate, etc.), is subjected to the irradiation of lasers of a wave length close to the maximum absorption wave length of the colorant used in such a way as to explode the diazonium perchlorate in the irradiated part and then to the irradiation of ultraviolet rays in such a way as to inactivate the diazonium perchlorate in the part not irradiated with lasers. By this, stable recording can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording method using diazonium perchlorate as a constituent component of a recording medium.

BACKGROUND ART Hitherto, regarding recording methods, methods using recording media containing photosensitive, heat-sensitive or pressure-sensitive compounds as constituent components have been developed and put into practical use. Recently, recording media capable of recording with laser light have been applied to a wide range of applications such as memories, microfilms, and laser printers. Attempts have been made to use easily decomposable compounds such as cellulose as one type of recording medium for such laser light. That is, He-IJe is applied to a recording medium in which nitrocellulose containing a dye that absorbs laser light, such as brilliant green, is coated on the base layer.
This is a method of recording by irradiating a laser beam such as , causing the nitrocellulose in the irradiated area to explode. However, although this method has a high recording sensitivity, it has the problem that the recording medium is unstable even after recording because it remains active against heat and impact.

In the course of research on diazonium compounds, the present inventor
Diazonium perchlorate has the property of decomposing (exploding) extremely easily due to heat, impact, etc. Also, the diazonium group is decomposed by violet 114F# irradiation and is inactivated against heat and impact. As a result of our efforts to utilize this knowledge in a laser beam recording medium, we have completed the present invention.

That is, an object of the present invention is to provide a laser beam recording medium and a recording method using the same.

To summarize the present invention, the present invention provides a recording medium provided with a layer containing diazonium perchlorate and a dye having absorption characteristics having a maximum absorption wavelength of 450 nm or more on a base material.
Laser light with a wavelength close to the maximum absorption wavelength of the dye is irradiated to explode the diazonium perchlorate in the irradiated area, and then ultraviolet rays are irradiated to detonate the diazonium perchlorate in the non-irradiated area. The present invention relates to a recording method characterized by activation.

The diazonium perchlorate used in the present invention has the partial formula Ar
-NZ" 0104- (where Ar represents an unsubstituted or substituted aryl group), some of which are known compounds.The explosive properties of this compound due to heat and impact have not been determined qualitatively. It was known as
Degradability by light has not yet been investigated.

Therefore, it was completely unexpected to use biazonium perchlorate as a substitute for the known nitrocellulose mentioned above.

By the way, 1. the present inventor has discovered p-diazo-N, N-dimethylaniline perchlorate (hereinafter referred to as compound A), p-diazo-N, N-diethylaniline perchlorate (hereinafter referred to as compound B), and 2- Methoxy-5-nitrobenzenediazonium perchlorate (hereinafter referred to as compound C) was synthesized, and the ignition point and minimum critical pressure (
(by pure shock wave detonation method) was measured in comparison to lightning and diazodinitrophenol. The results are shown in the table below.

Table As is clear from this table, Compound A-0 both has a lower ignition point and lower minimum pressure than the conventional Raikou and Diazodinitrophenol.

It has excellent explosive power. Since both of them are incurable to water, they have good moisture properties and excellent storage stability. A No. 6 DI) MP detonator was fabricated using the compound CO, , 29, and using this, TN'r I Kg could be easily detonated.

In addition to the explosiveness, moisture resistance, and storage stability of diazonium perchlorate, which are clear from the foot measurement results, the present invention also provides that the diazonium group decomposes when irradiated with ultraviolet light for 10 to 30 seconds. This method takes advantage of the characteristic of the surface that it does not cast shadows (4ii) in identifying dot-shaped recorded images.

Examples of the diazonium perchlorate of the present invention are as follows.

02H5 oc, n9 ”　　　OOHs 00, H.

00) T3 002 H5 o oc3Hs t 3O o2 0E3 A L ON, 0 1 1 stick CH3 00H.

0H3 O2 Many of the above diazonium perchlorates are easily produced by reacting the 112znot2 salt of the corresponding commercially available diazonium compound with perchloric acid or its lithium salt.6 Among the above diazonium perchlorates, As is clear from the above table, compounds containing nitro groups have a high oxygen content, making them highly explosive1. Also, the diazonium group in the molecule is photoactive, and is photosensitive to violet 91t7tB irradiation. Decomposes and loses explosive properties after photolysis.

As the dye (pigment compound) used in combination with diazonium perchlorine #salt, dyes with absorption at 450 nm or more are selected from the viewpoint of compatibility with the wavelength of laser light, examples of which include malachite clean and leuco crystal. Examples include violet, Congo red, methylene blue, and nigrosine NB. Although Naori-Bon black is not originally a pigment, it is included in this specification as a pigment because it is used in the same way.

The blending ratio (weight ratio) of diazonium perchlorate and the dye is 20 to 11:1, although it is not critical. A recording medium is constructed by providing these blended compositions as a layer on a base material such as glass, plastic, paper, or the like. For the formation of the layer, a method is generally adopted in which the above-mentioned formulation composition is applied onto the base I, so unless either the diazonium perchlorate or the dye has film-forming properties, the binder is generally applied to all of the above-mentioned formulations. It is added to the composition and also blended with a solvent. Suitable binders include polystyrene, vinyl chloride-vinyl acetate copolymers, acrylic polymers, and polyvinyl alcohol.

The laser light is a He-Nθ laser (emission wavelength 6
33nm) Ar laser (488nm), semiconductor laser (700-1500nm), etc.

Use a light source with an emission wavelength close to the maximum absorption wavelength of the dye used.

By laser light irradiation, the absorbed light energy is converted into heat, and this heat forms diazonium. When the recording medium is irradiated with ultraviolet rays after recording, the diazonium group is photodecomposed and the subsequent recording properties of the recording medium are lost. Suitable sources of ultraviolet light include mercury lamps, xenon lamps, fluorescent lamps, and the like.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto in any way. In the following examples, the compounds A to 0 described above were used.

Production Example of Compound A To 100 g of p-diazo-N, N-dimethylaniline chloride zinc chloride (Tokyo Kasei Reagent) solution of 5 g of diluted water, 5 ocx of 70 g of persalt acid diluted 10 times was added. . A yellow precipitate formed upon mixing. This was filtered through a glass filter, washed several times with water, and then vacuum dried in a chamber for 5 hours to obtain p-diazo-N,N-dimethylaniline perchlorate. It was a pale yellow-green powder, M# in water.

Production example of compound B: 100 ml of water in a 100 cc, three-lens flask equipped with a stirrer and a thermometer.
0 Cr,, N,N-diethyl/L=-p-phenylenediamine dihydrochloride4. Of, 36% salt rH2,q
Added cc. Add ice chips to the flask to lower the liquid temperature to 1-3℃.
As 32 t of sodium nitrite was added to the water bath, the bath solution gradually became diazonium salt.
exhibits a yellow color. The end of the reaction was confirmed by a slight change in color of the potassium iodide powder paper. 1N aqueous sodium carbonate solution was added to neutralize the per-1 hydrochloric acid. After this, add 70 thioperchloric acid diluted 10 times to 20CC,
p-Diazo-N,N-diethylaniline perchlorate was obtained as a yellow precipitate. Thereafter, the treatment was carried out in the same manner as in the above production example.

Preparation Example of Compound C 2-Methoxy-5-nitrobenzenedianium chloride 100% aqueous solution of zinc chloride (Daito Chemical System) 1 oocc
When 60Ω of a 10% aqueous solution of lithium perchlorate was added to the mixture, a yellow precipitate was produced.

The same treatment as in the above production example was performed to obtain 2-methoxy-5-nitrobenzenediazonium perchlorate.

Example 1 Compound A IOf vinyl chloride vinyl vinyl copolymer io f brilliant green 11 methyl ethyl ketone
1 [, 1OCCO West 1, 1], a composite composition was applied onto a glass substrate by a spinner method to a test thickness of about 1 μm, and dried to form a recording medium.

When this recording medium was irradiated with a He-Ne laser focused to a diameter of 2.8 μm, it was possible to record dot-shaped holes on the recording medium at 6 mW and for an irradiation time of up to 50 n8. Next, the recording property due to heat or shock disappeared after 30 seconds of illumination with a xenon lamp.

Examples 2 and 3 The same experiments were repeated except that Compounds B and C were used in place of Compound A in Example 1. The condition of the dot-like holes recorded was similar to that in Example 1.

Comparative example Nitrocellulose 10f brilliant green 1f methyl ethyl ketone
A 100CC blended composition was applied onto a glass substrate by a spinner method to a film thickness of approximately 1 pm, and dried to form a recording medium.

When this recording medium was irradiated with a He-Ne laser in the same manner as in Example 1, the formation of dot-like holes was not clear at an irradiation time of 50 ns (the formation of holes was only observed after 100 ns or more).

When the recording media of Example 1 and Comparative Example were left in an atmosphere of 40° C., 90% R, H, immediately after production, before recording, and after recording, the appearance of Example 1 remained unchanged even after a week or more had passed. There was no change in the recording medium of the present invention, but a tendency to become cloudy was observed in all of the comparative examples.From this, it is understood that the recording medium of the present invention is excellent in stability and storage property.

Patent applicant Hiroshi Nakamoto, agent for Nippon Telegraph and Telephone Public Corporation Procedural amendment (method) % formula % 1, Indication of case Patent Application No. 62476, 1982 2
, Title of the invention Relationship with the Recording Method 5 Amendment Case Patent Applicant Address 1-1-6 Uchisaiwai-cho, Chiyoda-ku, Tokyo
Name (422) Makoto, Representative of Nippon Telegraph and Telephone Public Corporation
Tsune Fuji Address: 502 Nishi-Shimbashi Chuo Pill, 6-15-8 Nishi-Shimbashi, Minato-ku, Tokyo Phone: (437)-3467 Name:
Patent Attorney (7850) Hiroshi Nakamoto 5 Date of amendment order: July 9, 1982 (Shipping date: July 27, 1980)
& Subject of amendment Full text of the specification

Claims (1)

[Claims] 1. Diazonium persalt folate and maximum absorption wavelength is 45
A recording medium provided with a layer containing a dye having an absorption characteristic of 0 nm or more on a base material is irradiated with a laser beam having a wavelength close to the maximum absorption wavelength of the dye, and the diazonium perchlorate in the irradiated area is removed. A recording method characterized by detonating and first irradiating ultraviolet rays to inactivate the diazonium perchlorate in the part not irradiated with laser light.