JPH0133357B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a recording material having a recording layer that is thermally deformed by irradiation with high-density energy light. When irradiated with high-density energy light such as a laser beam, the recording layer undergoes thermal deformation such as melting, evaporation, and aggregation due to the heat of the high-density energy light, and the optical characteristics of the deformed area change. Thermal (heat mode) recording materials in which information is recorded by changes are known. As a method of irradiating high-density energy light in such a recording method on a thermal recording material, for example, the information to be recorded is converted into an electrical time-series signal, and the intensity of the laser light is modulated according to the signal. , a method of scanning the recording material with the modulated laser light, a method of irradiating the recording material with a two-dimensional optical information carrier, and irradiating the recording material with strobe light or scanning laser light, etc. However, in many cases thermal deformation occurs after only a very short period of irradiation, and in general, irradiation, that is, recording is complete, and post-processing such as development is not required. Inexpensive materials such as metals, dyes, and plastics can be used as the recording layer of such thermal recording materials, but materials with high recording sensitivity include those using specific metals and those with various layer configurations. Are known. For example, Japanese Patent Publication No. 46-40479 discloses a recording layer composed of three layers of germanium, bismuth, and selenium. Here, the germanium layer reduces the reflectance of the bismuth layer to irradiated light, and the selenium layer is a layer that evaporates easily, and both can be used as the main recording layer with less energy than in the case of a single bismuth layer. Accelerate thermal deformation of certain bismuth layers. Furthermore, a layer for reducing or preventing reflection was developed in JP-A-50
It is also described in Publication No.-151151 and Japanese Patent Publication No. 51-14263. In addition, a layer provided with a layer for reducing heat conduction between the recording layer and its support was disclosed in Japanese Patent Application Laid-Open No.
It is described in Publication No. 126237 and Japanese Unexamined Patent Publication No. 16026/1983. Also, the patent application filed in 1973 by the present inventors, etc.
-78236 and JP-A-52-20821 disclose recording layers in which metal sulfides, metal fluorides, or metal oxides are layered or mixed with metal, and JP-A-53-83617 describes describes a recording layer in which a halide is layered or mixed with a metal. As a result of further intensive research, the present inventors discovered a new recording material with a sensitivity equal to or higher than that of the above-mentioned recording materials, which led to the present invention. It is an object of the present invention to provide a highly sensitive thermal recording material. Another object of the present invention is to provide a highly sensitive thermal recording material with excellent recording image quality. Another object of the present invention is to provide a highly sensitive recording material without the risk of causing pollution. A further object of the present invention is to provide a highly sensitive recording material that is inexpensive and requires fewer manufacturing steps. That is, in the present invention, the recording layer, which is provided on a substrate and undergoes thermal deformation when irradiated with high-density energy light, is formed by sequentially stacking a metal as the first layer, an organic material as the second layer, and a metal as the third layer by vapor deposition. This is a recording material characterized by a recording layer consisting of: In the present invention, evaporation refers to methods including vacuum evaporation using an ordinary resistance heating method, vacuum evaporation using an electron beam heating method, sputtering, ion plating, plasma deposition, and the like. The substrate used in the present invention may be the same as the substrate of conventionally known general recording materials such as plastic, paper, glass, etc. Further, the high-density energy light may be a focused laser light such as a strobe light that thermally deforms the recording layer of the recording material. Thermal deformation refers to deformation caused by melting, evaporation and agglomeration, or other forms of heat. It is sufficient that the deformation is such that it has a detectable difference. Various metals can be used as the metal used in the present invention, and for example, metals disclosed in Japanese Patent Application Laid-Open No. 52-20821 may be used.
Mg, Mn, Cu, Zn, Al, In, Sn, Bi, etc. are preferable. In particular, those with low touch point and temporary reflectance,
Preferred metals include Sn and Bi. These metals may be used alone, in combination of two or more, or in the form of an alloy in the present invention. Further, the metal used for the first layer and the metal used for the third layer may be the same,
They can be different. There are various organic substances that can be used in the present invention. The necessary conditions for these organic substances are that they are solid at least at room temperature and have properties that allow vacuum deposition. It is preferable that the melting point, sublimation temperature, etc. be as low as possible, but it is preferable that the substance has good stability before or after vapor deposition. However, in the case of organic substances, their melting point and sublimation temperature are often around 350°C, so almost any organic substance can be used. For example, organic carboxylic acids are preferred organic substances used in the present invention, including higher fatty acids such as behenic acid, stearic acid, palmitic acid, myristic acid, phthalic acid,
Carboxylic acids with aromatic rings, such as isophthalic acid, pyromellitic acid, anisic acid, coumaric acid, and cinnamic acid; polycarboxylic acids, such as fumaric acid, succinic acid, sebacic acid, oxalic acid, and pimelic acid. , abietic acid and the like are preferred. Salts and esters of these acids are likewise preferred. Aromatic sulfonic acids such as sulfanilic acid are also preferred organic materials. Polymeric compounds are also preferred organic materials, such as polymethacrylic acid, polystyrene,
Examples include nylon, polyvinyl alcohol, polyethylene oxide, methyl cellulose, polyvinyl butyral, polymethyl methacrylate, polyisobutyl methacrylate, polyethylene, and rosin resin. Organic acyclic sulfur compounds are also preferred organic substances, such as thiourea and its derivatives, thiosemicarbazides and their derivatives such as dithizone, thiocarbamic acids and their derivatives such as diethyldithiocarbamic acid, thiobenzophenones and their derivatives. . Heterocyclic compounds containing nitrogen or sulfur are also preferred organic substances, such as imidazoles and their derivatives such as benzimidazole and 2-mercaptobenzimidazole, triazoles such as benztriazole and their derivatives, tetrazoles such as mercapto and phenyltetrazole, and their derivatives. derivatives etc.
There are thiazoles and their derivatives such as benzthiazole, 2-mercaptobenzthiazole, and 2-aminobenzthiazole. Furthermore, pyrimidine bases contained in nucleic acids, such as cytosine, uracil, thymine, 5-methylcytosine, and oxymethylcytosine, are nontoxic and are preferably used. These organic substances may be used alone or in appropriate combinations in the present invention. The recording material of the present invention will be explained below with reference to the drawings. 1 to 4 are cross-sectional views of conventionally well-known thermal recording materials, and FIG. 5 is a cross-sectional view of one example of the recording material of the present invention. Throughout each figure, 1 is a substrate, 2 is a metal layer, 3 is an antireflection layer, 4
5 is an organic material layer, and 5 is a mixed layer of metal and inorganic or organic material. In the recording material of the present invention (FIG. 5), the substrate 1
A first layer of metal 2 is provided in contact with the first layer, a second layer of organic material 4 is provided on the first layer, and a third layer of metal 6 is provided on the second layer. The metal 2 of the first layer in the recording material of the present invention (FIG. 5) is similar to the metal 2 or the mixed layer 5 of metal and an inorganic compound or an organic compound in the known recording material (FIGS. 1 to 4). It mainly determines the optical density of the recording material. The film thickness of the first layer of metal 2 is 100 to 5000A, preferably 200 to 2000A, but it may vary depending on the optical properties of the metal, other physical and chemical properties, manufacturing conditions, or the use of the recording material. , can be determined appropriately. In the present invention, by sequentially laminating the organic substance 4 of the second layer and the metal 6 of the third layer on the first layer, it is possible to reduce the reflectance of the high-density energy light required for recording, and to reduce the reflectance of the irradiated light. The recording layer can absorb effectively. The reason why the reflectance decreases when an organic substance and a metal are sequentially laminated is not necessarily clear, but when the third layer of metal 6 is provided on the second layer of organic substance 4 by vapor deposition, the organic substance and metal are It is thought that the reflectance decreases due to some kind of interaction, or because the metal is vapor-deposited on the organic substance, causing the metal to be dispersed into minute islands. The thicknesses of the second and third layers vary depending on the type of organic material, type of metal, manufacturing conditions, etc., but can be appropriately selected so that the reflectance of the recording material is minimized. The thickness of the second layer of organic substance 4 is 10A~
3000A, preferably 50A to 500A, and the thickness of the third layer metal 6 is 10A to 2000A, preferably 30A to
It is 500A. The first layer metal, the second layer organic substance, and the third layer metal do not have a so-called layered structure, but may have an island structure or a structure in which they partially react with each other, and do not need to have a uniform layered structure. Since organic substances generally have poor thermal conductivity, it is difficult for the light to escape from the irradiated area, so the absorbed heat is effectively used to thermally deform the recording material in that area. Further, since the recording material in the thermally deformed area is an organic substance, it easily aggregates into small spheres, so the boundary between the recording trace and the non-irradiated area is clear, so that recording with good resolution can be achieved. Furthermore, the metals and organic substances constituting the recording layer of the present invention have almost no toxicity, are inexpensive, and can be manufactured entirely by vapor deposition, which simplifies the manufacturing process and makes it possible to obtain a highly sensitive recording material. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Example 1 On a polyethylene terephthalate substrate with a thickness of 100 μm, 300 A of Sn was vapor-deposited at a vacuum degree of 5×10 ⁻⁵ torr.
Next, polyethylene (manufactured by Sanyo Kasei, Sanwax) was evaporated at 300A in the same vacuum equipment, and Sn was further deposited.
A sample of the present invention was prepared by vapor deposition at 100A. Comparative sample 1 is a sample in which Sn is vapor-deposited at 300A, comparative sample 2 is a sample in which Sn is vapor-deposited at 300A, and then polyethylene is vapor-deposited.
A sample with 300A vapor deposition was prepared. Argon ion laser light (wavelength 5145A) was focused on these recording materials to a diameter of 25 mm, and the scanning speed was 19.
Recording was performed by irradiating at m/sec to cause thermal deformation and lowering the transmission density of the irradiated area. The minimum output intensity of the laser beam required for this recording (hereinafter referred to as threshold value) was determined, and the relative sensitivity of each recording material was evaluated based on the magnitude of this threshold value. Since the recording material according to the present invention has a threshold value required for recording smaller than 1/3 of Comparative Sample 1 and Comparative Sample 2, an increase in sensitivity of more than 3 times was obtained by the present invention. 1st
The above results and the transmission density for visible light are shown in the table.

[Table] Example 2 On a polyethylene terephthalate substrate with a thickness of 100 μm, 300 A of Sn was vapor-deposited at a vacuum degree of 5×10 ⁻⁵ torr.
Next, 200A of uracil was deposited in the same vacuum device,
Furthermore, In was vapor-deposited at 80A. As comparative sample 3, Sn
A sample was prepared in which GeS was evaporated for 300A and GeS was further evaporated for 200A on top of it. Sensitivity evaluation was performed in the same manner as in Example 1, and as shown in Table 2, the samples of the present invention had a threshold value.
100 mW, and comparative sample 3 had a power of 125 mW, indicating that the recording material of the present invention had a higher sensitivity by 20% or more.

【table】 [Brief explanation of drawings]

1 to 4 are cross-sectional views of known recording materials, and FIG. 5 is a cross-sectional view showing the layer structure of the recording material of the present invention. In the figure, 1 is a substrate, 2 is a metal layer, 3 is a metal or inorganic or organic antireflection layer, 4 is an organic layer, 5 is a mixed layer of metal and inorganic or organic material,
6 indicates a metal layer as the third layer of the present invention.

Claims (1)

[Claims] 1. A recording layer provided on a substrate that causes thermal deformation when irradiated with high-density energy light is formed by sequentially stacking a metal as the first layer, an organic material as the second layer, and a metal as the third layer by vapor deposition. 1st layer and 3rd layer
The layer metals are Mg, Mn, Cu, Zn, Al, In, Sn and
Bi selected from the group consisting of Bi and each having a film thickness of 200
~2000A and 30~500A, and the thickness of the second layer is
Recording material characterized by being 50-500A.