JPH01274129A - Novel recording material - Google Patents

Abstract

PURPOSE:To make it possible to form an accurate image with a simple laser device by using the silver salt of specified sulfonic acid as a base. CONSTITUTION:The silver salt of sulfonic acid having at least 0.6 ratio of the absorbance of a strong band at about 1,200 wave number in the infrared absorption spectrum to that of a band due to a sulfonic acid group at about 1,050 wave number is used as a base. Since the silver salt of polyenesulfonic acid is sensitive to light and/or heat and deposits metallic silver, the simple laser device can be used. When the silver salt is irradiated with laser light, the irradiated part causes a chemical reaction at once and forms metallic silver, so an accurate image can be formed without requiring troublesome operation. The silver salt can be produced at a low cost by chemically treating a high molecular compd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel photosensitive and/or heat-sensitive recording material based on a silver salt of sulfonic acid.

More specifically, the present invention relates to a new photosensitive material that is sensitive not only to ultraviolet light but also to low-power laser light in the visible and near-infrared regions.

[Prior Art] In recent years, instead of the phototypesetting method, a method of directly outputting an article, etc. edited using a computer onto a negative film or the like has been attracting attention. This method records time-series digital signals output from a computer, and in practice it uses low-power visible laser light such as a helium-neon laser or argon laser, or low-power laser light such as a semiconductor laser. Materials that are sensitive to this must be used. Therefore, as a way to deal with these problems, methods have been taken to improve the conventional silver halide film so that it is highly sensitive and sensitive to long wavelength light, but this method is not only expensive but also has poor storage stability. This method has drawbacks such as the need to employ a complicated wet phenomenon method. On the other hand, as recording materials for information output from computers, vapor-deposited thin films of bismuth, tellurium, chalcogenide, etc., and materials in which an anthraquinone or methine dye layer is provided on a polymer substrate have been put into practical use. These are based on physical changes caused by local heating with laser light; the former melts and aggregates, making this area transparent and recording information, and the latter uses thermal diffusion of the dye. This is an application of the fact that the absorption spectrum of dyes changes depending on the color of the dye. In other words, it records physical changes caused by heat and detects them as differences in light transmittance and refractive index, which not only often causes errors but also has a resolution that is impractically low, on the order of a few microns. . Furthermore, in general, in forming the recording layer, it is necessary not only to employ a complicated and low-productivity method such as vapor deposition, but also to form various undercoat layers, reflective layers, etc.

[Problem of the Invention and Means for Solving the Problem] The object of the present invention is to provide a new recording material which is free from the double drawbacks and is suitable for modern uses.

That is, the present invention has a wave number of 120 in the infrared absorption spectrum.
A recording material based on a silver salt of sulfonic acid, characterized in that the ratio of the absorbance of a strong band near 0 to the absorbance of a band attributed to a sulfonic acid group near a wavenumber of 1050 is at least 0.6. Since it is sensitive not only to ultraviolet light but also to visible and near-infrared light from low mountain horns, simple laser devices such as helium-neon lasers, argon lasers, or semiconductor lasers can be used. This is the characteristic. Surprisingly, the area irradiated with the laser light immediately undergoes a chemical reaction to produce metallic silver, which eliminates the need for complicated operations like conventional wet development, and allows the formation of precise images. Furthermore, it has the characteristic that it can be manufactured at an extremely low cost by chemically treating a polymer compound as described below.In addition, this abrasive material can be made into a film or a disk, Information output from a computer can be written using the laser beam, and an inexpensive material that can be recorded with high precision can be provided.

The present invention provides a compound that has at least three or more conjugated double bonds and a silver salt of sulfonic acid adjacent to the double bond, that is, a silver salt of polyenesulfonic acid that is sensitive to light and/or heat. It was completed by discovering that metallic silver can be deposited. The amount of the sulfonic acid silver salt can be determined from the ratio of the absorbance of a strong band around 1200 wave numbers to the absorbance around 1050 wave numbers in the infrared absorption spectrum. When the absorbance ratio is 0.6 or more, it is possible to provide a material that is sensitive to the laser beam and can be identified or read. That is, the sensitivity below 066 is not sufficient and is therefore excluded. Further, the absorbance ratio within the range obtained by a normal sulfonation reaction is 2.3, and it is generally difficult to obtain a product having an absorbance ratio higher than that.

Examples of the polymer compounds used in the present invention include ethylene, propylene, butene-1,4-methylpentene-
Examples include homopolymers of olefins such as 1, hexene-1 and octene-1, and/or mutual copolymers of the above monomers with a molecular weight of at least 10,000 or more.

High-density polyethylene (density 0.94 to 0.97) produced by a low-pressure method or a medium-pressure method is particularly suitable. In addition, as polymer compounds, for example, vinyl chloride, vinylidene chloride,
Vinyl fluoride, vinylidene fluoride, ethylene trifluoride,
One or more monomers selected from vinyl halides or vinylidene halides such as propylene hexafluoride and vinyl bromide are polymerized, or other monomers such as ethylene, propylene, butene-1, When the main material is one obtained by copolymerizing with at least one type of hexene-1, etc., the disadvantage is that the sulfonation rate becomes slower as the proportion of the unsaturated halogen compound increases in the sulfonation reaction. However, it is practically preferable because the resulting compound having a silver salt of sulfonic acid has greater photosensitivity.

In addition, acrylonitrile as a monomer having a polar group,
Nitrile groups such as methacrylonitrile, ethyl acrylate, methyl acrylate!・Polymerize one or more monomers selected from olefin compounds having ester groups such as olefin compounds and acetate groups such as vinyl acetate, or polymerize other monomers such as ethylene, propylene, butene.
Examples include polymer compounds obtained by copolymerizing with at least one type of hexene-1 and the like.

One method for producing polyenesulfonic acid according to the present invention is to produce a film, sheet or disk of a polymeric compound containing at least one type of polymeric compound as a main material selected from the above-mentioned polymeric compounds having a number average molecular weight of 10,000 or more. A sulfonation reaction is carried out using an oxidizing sulfonating agent such as fuming sulfuric acid or sulfuric anhydride. There are no particular restrictions on the method of sulfonation; for example, the sheet may be immersed in fuming sulfuric acid, or the sheet may be immersed in sulfuric anhydride as it is, or in sulfuric anhydride such as chloroform, carbon tetrachloride, or ethylene dichloride. On the other hand, it may be used after being diluted with a 6-component solvent that has relatively low activity. Further, sulfonation may be carried out as an adduct of sulfuric anhydride with dimethylformamide, dioxane, or the like. Sulfonation conditions vary depending on the type of polymer used, but in general, when the reaction is performed using an oxidized sulfonating agent such as sulfuric anhydride, a structure with an infrared absorption spectrum band around 1200 wave numbers is obtained. are easy to generate. In particular, in order to obtain the recording material of the present invention with excellent photosensitive and heat sensitive properties, the reaction temperature is -30 to 70°C, preferably 30°C or lower. Suitable for increasing the production ratio of sulfonic acid.

On the other hand, if the reaction temperature is 130° C. or lower, the rate of the sulfonation reaction is slow, so it is excluded. Generally, the amount of sulfonation increases as the sulfonation reaction progresses, but the ratio of absorbance is not necessarily linear with the amount of sulfonation, so optimal conditions must be selected for each polymer, but preferably. The amount of sulfonation is 5 x 10 in terms of exchange equivalent.
It is 1×10 −1 m/cJ. 5 x 10-”
Below millimeter ffl/c+&, the amount of silver salt introduced by reaction with the silver nitrate aqueous solution is insufficient, and the density of the image produced by scanning with a laser or the like is small, so it is removed. In addition, under the conditions for introducing sulfonic acid groups of I×10 −1 m/Q or more, the surface of the film is partially carbonized due to a side reaction and is therefore excluded. Incidentally, the amount of sulfonation is determined as follows. That is, a film with a sulfonated surface (surface area Men?) is immersed in a 1N calcium chloride aqueous solution to reach an equilibrium state, and the hydrogen chloride generated in the aqueous solution is
Titrate with 0.1N aqueous sodium hydroxide solution (potency: f) to determine the neutralization value (X
cc) and calculate it using the following formula.

Sulfonated ff1-(0, lx f xX) /M (milliequivalents/C♂) The absorbance ratio here is determined using a baseline method that is generally employed in the analysis of infrared absorption spectra. That is, the absorbance ratio of the strong bands around wave numbers 1050 and 1170 attributed to sulfonic acid groups and the strong bands around wave numbers around 1200 defined by the present invention is determined based on a common baseline. In addition, the infrared absorption spectrum of the sulfonate is determined by the reflection method (ATR method).
It can be measured by It is known that sulfonic acid groups normally exhibit two characteristic strong bands near wave numbers 1050 and 1170;
The above-mentioned sulfonated product exhibits a similarly strong band around 00, preferably around 1200 to 1230 wave numbers,
When the ratio of the absorbance of a band around wave number 1200 to the absorbance of a band attributed to a sulfonic acid group around wave number 1050 is 0.6 or more, recording sensitive to laser light, thermal heads, etc., which is the object of the present invention. Offer a shrine. It is generally difficult to obtain an absorbance ratio of 2.3 or more, and the absorbance of a sulfonated product having the sensitivity necessary to form an image using a commonly used recording method is preferably 1.1.
~1.8.

The thus obtained polyenesulfonic acid is further treated with an aqueous solution of silver nitrate to improve the photosensitivity and/or sensitivity of the present invention.
Alternatively, heat-sensitive materials can be provided. The concentration of the silver nitrate aqueous solution is usually 3N or less, and may be in an amount sufficient to rapidly perform ion exchange with the polyenesulfonic acid.

The photosensitive and/or heat-sensitive film or sheet containing the silver salt of polyenesulfonate thus obtained can be used as is, or it can be attached to other substrates, such as paper, polyester film or sheet, or a board made of polycarbonate or aluminum. It may also be used as a laminated composite material.

[Implementation example] The present invention will be specifically explained below with reference to Examples.

Example 1 In a dry glass container, size lO10X15. A reaction vessel set with a high-density polyethylene film (14 average molecular weight approximately 100,000) with a thickness of approximately 200 μm was heated to an internal temperature of 0 to
It was externally cooled to 5°C. On the other hand, S03 gas/nitrogen gas (volume ratio 1/2) was adjusted to be 1 liter per minute and was introduced into the reaction vessel for 25 minutes to carry out the reaction. After the reaction was completed, the film was taken out from the container, washed with water, further treated with a 1N aqueous solution of silver nitrate, and then dried.

The amount of sulfonation of this film was 7.2×10' mm/ffl/cd, and the absorbance ratio of the infrared absorption spectrum was 1.7. Next, the above film was attached to an aluminum roll, and a helium-neon laser (manufactured by NEC Corporation, GL 5400, output 10 mw) was used in the same manner as in Example 1.
) (7) When scanning was carried out while irradiating light condensed to a beam diameter of 5 μm at a roll circumferential speed of 50 cm/see, a clear black image with a line width of 5.1 μm was obtained.

Example 2 The high-density polyethylene film used in Example 1 with a thickness of approximately 200 μm was set at a predetermined reaction temperature and reaction time, and was sulfonated, washed with water, and treated with an aqueous silver nitrate solution according to the method of Example 1. It was then air-dried. Next, the writability was tested by scanning with a helium-neon laser in the same manner as in Example 1, and the results shown in the following table were obtained.

(Space below) Example 3 The high-density polyethylene film used in Example 1 with a thickness of about 200 μm was immersed in fuming sulfuric acid containing about 15% by weight of sulfuric anhydride at 0°C for about 20 hours to undergo a sulfonation reaction. I did it. After the reaction was completed, it was thoroughly washed with water, treated with a 1N silver nitrate aqueous solution, and then air-dried. The amount of sulfonation of this film was 8.2 Xl0-3 meq/cJ, and the absorbance ratio was 0.7.

Next, this film was attached to the aluminum roll used in Example 1, and Yag Racer (NEC; 5L129, output 5
When writing was carried out by scanning light focused on a beam diameter of 10 μm at a roll circumferential speed of 100 cm/see, a clear image with a line width of 10.2 μm was obtained.

Example 4 Commercially available polyvinyl chloride film (manufactured by Sumitomo Bakelite Co., Ltd.; Sumilite VSS, water absorption rate 0.1
%, size LOX 15 cm) was set in a dry glass container in the same manner as in Example 1, and the sulfonation reaction was carried out. The reaction time was 45 minutes. After the reaction was completed, the film was taken out from the container, thoroughly washed with water, treated with a 1N aqueous silver nitrate solution, and then dried.

The amount of sulfonation of this film is 2.3X10-''3mm/cJ, and the absorbance ratio of the infrared absorption spectrum is 1
．． It was 2. The above film was attached to a roll in the same manner as in Example 1, and the peripheral speed of the roll was set to 1200 cm/see.
When scanning was performed with the setting set to , a clear black image with a line width of 5.04 m was obtained. Furthermore, when printing was performed using a thermal head using a word processor (manufactured by Sharp Corporation; "Shoin", model WD-300F), the printed portion became a clear black image.

Example 5 Ethylene, 4-methylpentene-1 with a thickness of about 150 μm
(3 mol 9.6) linear low density polyethylene film (
2 under the same reaction conditions as in Example 1.
After carrying out the sulfonation reaction for 0 minutes, it was washed with water, treated with a 2N silver nitrate aqueous solution, and then air-dried. The amount of sulfonation in this film is 1.4 x 10-3 mm/ct
J, and the absorbance ratio was 1.2.

The film thus obtained is pasted on a rotating roll,
A semiconductor laser (
Manufactured by Sharp Corporation, LT027 MDIMF.

When the laser beam was focused with an optical lens and scanned, the area scanned by the laser beam was identified as a black line. The line width was 4.3 μm.

[Effects of the Invention] The recording material of the present invention is sensitive to low-power light sources, can be used with a simple laser device, is inexpensive and easy to use, and has excellent effects in that it can form precise images. .

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] 1. A silver salt of sulfonic acid, characterized in that the ratio of the absorbance of a strong band around wave number 1200 to the absorbance of a band attributed to a sulfonic acid group around wave number 1050 in an infrared absorption spectrum is at least 0.6. Recording materials mainly composed of