JPH0465793B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a laser recording film suitable for recording using laser light. In recent years, many methods using laser light have been proposed in fields where high-speed or real-time recording of information is required. This method utilizes the intensity and resolution of the optical energy of laser light, and the laser light is irradiated onto a material with good light absorption, and the material that absorbs the laser light and is heated is deposited on the image receiving surface. It records images. [Prior Art] As this recording film, a recording film coated with a coating material containing heat-absorbing microparticles such as carbon black and a self-oxidizing binding substance such as nitrocellulose has been proposed (Japanese Patent Application Laid-Open No. 1983-1972). −43632). This recording film enables negative and positive recording by irradiating it with laser light and transferring fine particles such as carbon black to other recording tapes. Also applying to the transparent film a coating material consisting of particles that absorb laser energy, a self-oxidizing binder and a cross-linking agent or a cross-linking agent in combination with a cross-linkable resin or a non-oxidizing polymeric substance or resin; A method has been proposed in which a printing plate is produced by bringing this into close contact with a lithographic printing surface such as an aluminum sheet, and introducing laser light from the transparent film side to selectively transfer the coating material to the lithographic printing surface. (Japanese Patent Application Laid-Open No. 102402/1973).
All of these laser recording films utilize a self-oxidizing binder such as nitrocellulose, and the heat supplied by the laser beam heats the self-oxidizing binder, causing it to burn or eject, producing carbon black. The heat-absorbing particles and resin are carried out, leaving a plain area on the film or recording an image on the image receiving surface. However, as mentioned above, self-oxidizing binders such as nitrocellulose are used in the binder resins used in the manufacture of these laser recording films and image-forming printed boards, so they can become acidic due to thermal decomposition during the process. The disadvantages are that substances are generated that corrode the system, there are concerns about safety during storage, and the resolution is poor. Furthermore, the recording layer (recording medium layer) of these laser recording films is easily scratched, and the coating film thickness is approximately
Because it was as thin as 0.5 μm, scratches easily reached not only the surface of the recording layer but also the surface of the substrate. The inventors of the present invention have made extensive studies to solve these drawbacks, and have found that a high blackening density can be achieved by using a non-self-oxidizing binder as a binder and further using graphite as heat-absorbing fine particles. can be used for further recording.
By containing a heat ray absorber that has a strong absorption ability in the wavelength range of YAG laser light, it is possible to make it easier to transfer the recording medium to the transfer image receiving surface of paper, printing plates, etc., and to prevent the recording medium from remaining on the transparent substrate. It has been discovered that it is possible to obtain a laser recording film that gives high-resolution negative and positive images without leaving any traces, and that by providing a protective layer made of organic polymer on the surface of the recording layer, it is possible to obtain a laser recording film that can produce high-resolution negative and positive images. It was discovered that it was possible to obtain a laser recording film with remarkable scratch resistance compared to recording films, and the authors published Japanese Patent Application No. 59-41724.
The application was filed as Japanese Patent Application No. 112311/1983. When a protective layer is provided, it is possible to improve the scratch resistance and chemical resistance of the recorded portion of the recording film, but this increases the thickness of the entire coating film and causes a problem of decreased recording sensitivity by laser. The scratch resistance is also affected by the material of the protective layer, but generally the scratch resistance improves as the film thickness increases. Furthermore, the recording sensitivity by laser is good as long as the coating film is thin, and image forming performance and scratch resistance are inversely proportional. When a protective layer is provided, when laser light is irradiated from the support side, heat attenuation occurs between the recording layer and the protective layer, which affects transferability.
This may result in a decrease in resolution. [Means for Solving the Problem] As a result of intensive studies to solve these problems, the inventors of the present invention have created a structure in which both the recording layer and the protective layer have strong absorption ability in the wavelength range of the laser light used for recording. The present inventors have discovered that a laser recording film having remarkable image forming properties and scratch resistance compared to conventional laser recording films can be obtained by incorporating a heat ray absorbing agent having a heat ray absorbing agent. That is, in the present invention, a recording medium layer containing a non-self-oxidizing binder resin and fine particles that provide a high blackening density and absorb heat is provided on a transparent substrate, and a protective layer made of a thermoplastic polymer is further provided thereon. The present invention provides a laser recording film characterized in that both the recording medium layer and the protective layer contain a heat ray absorber having a strong absorption ability in the wavelength range of the laser light used for recording. be. [Function] As shown in FIG. 1, the laser recording film of the present invention has a structure in which a non-self-oxidizing binder and a high blackening density are provided on a laser-transmissive support 1, and then heat is applied. A layer (recording layer) 2 coated with a recording medium containing absorbing fine particles and a heat ray absorber having a strong absorption ability in the wavelength range of the laser beam used for recording, and a solvent-soluble polyester layer on the recording layer 2. A protective layer 3 made of resin is provided. As shown in FIG. 2, the recording method is to scan and guide a laser beam adjusted through a normal lens system and adjustment device from the support 1 side, and transfer the recording layer (transfer supply body) 2 to the transfer image receiving body 4. A method of recording an image by depositing it on the image receiving surface can be used. It is desirable to attach the image receiving surface in contact with the protective layer 3, and if the degree of adhesion is improved by reducing the pressure, the resolution will be much better. According to this method, the transfer image receptor 4 can be transferred in one operation.
A positive image can be obtained on the recording layer 2 and a negative image can be obtained on the recording layer 2 at the same time. The negative film can be used when making a printing resin plate, and the positive image can be used as a proof copy or a direct printing plate depending on the type of transfer image receptor 4. The support for the laser recording film of the present invention may be any film that transmits laser light, such as polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polypropylene, polycarbonate, nylon-6, polyether sulfone, etc. can be mentioned. In particular, biaxially stretched films of polyethylene terephthalate and polypropylene are preferred because they have excellent transparency, strength, and dimensional stability. Examples of fine particles that absorb heat in the recording layer and achieve high blackening density include graphite and carbon black, which can be used alone or as a mixture. In particular, fine powder graphite is suitable as a material capable of imparting high blackening density in a thin film. Examples of the heat ray absorbent contained in both the recording layer and the protective layer of the present invention include compounds represented by the following general formula () or (). General formula () (Here, R is hydrogen or a lower alkyl group, X is an anion selected from the group consisting of hexafluoroarsenate ion, hexafluoroantimonate ion, fluoroborate ion, and perchlorate ion, and m is 0 or an integer of 1 or 2. A is

[expression] or

〔Effect of the invention〕

The laser recording film of the present invention is a real-time recording that does not require post-processing such as development and fixing, and is not exposed to light, so darkroom operations are not required, and it can be used for communication and computer processing information, which are rapidly developing in recent years. It is ideal for direct recording and can be widely applied. [Example] Hereinafter, the present invention will be explained with reference to Examples. All parts in the examples represent parts by weight. Example 1 Using the following graphite dispersion (formulation 1)
It was applied onto a 100μ polyester film using a Mayer bar and dried at 90°C to form a recording layer. A liquid mixture consisting of Formulation 2 was applied onto this recording layer by a dip method and dried at 90°C to form a protective layer. Dry thickness, blackening density and Nd-YAG laser (wavelength 1064nm output 10W 0.5Joule/on recording medium)
cm ² ) irradiation test results are summarized in Table 1. Formulation 1 Graphite 100 parts Ethylcellulose 36 parts Ethyl acetate 1224 parts Bis(P-diethylaminophenyl)
13.6 parts [N,N-bis-(P-diethylaminophenyl)-P-aminophenyl] Aminium hexafluoro antimonate Formulation 2 Solvent-soluble polyester resin 100 parts (“Vylon 200” manufactured by Toyobo Co., Ltd.) Methyl ethyl ketone 900 parts Bis(P-diethylaminophenyl)
10 parts [N,N-bis-(P-diethylaminophenyl)-P-aminophenyl] Hexafluoroantimonate of aminium Example 2 A Mayer bar was applied onto a 100μ polyester film using a graphite dispersion consisting of the following formulation 3. It was coated at 90°C and dried to form a recording layer. A liquid mixture consisting of Formulation 2 was applied onto this recording layer by the dip method and dried at 120°C to form a protective layer.
Dry film thickness, blackening density Nd-YAG laser (wavelength 1064nm output 10W on recording medium layer)
The results of the imaging test using 0.5 Joule/cm ² irradiation are summarized in Table 1. ) Formulation 3 Graphite 100 parts Ethylcellulose 36 parts Ethyl acetate 1224 parts Bis(P-dibutylaminophenyl)
6.8 parts [N,N-bis-(P-diethylaminophenyl)-P-aminophenyl] Aminium perchlorate Formulation 4 Styrene-butadiene copolymer 100 parts (Good-Year “PLIOLITES-”)
5B”) Toluene 900 parts Bis(P-dibutylaminophenyl)
6.8 parts [N,N-bis-(P-dibutylaminophenyl)-P-aminophenyl] Aminium perchlorate comparative example In Example 1, bis(P-diethylaminophenyl) [N , N-bis-
A coated film containing no hexafluoroantimonate of (P-diethylaminophenyl)-P-aminophenyl]aminium was prepared as a comparative example. Dry film thickness, blackening density, Nd-YAG laser (wavelength 1064nm output 10W on recording medium)
0.5 Joule/cm ² is summarized in Table 1. )

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a laser recording film of the present invention, FIG. 2 is a schematic cross-sectional view of a recording device using the film of the present invention, and FIG. 3 is a diagram showing a measuring method for a scratch resistance test. . 1... Support, 2... Recording layer, 3... Protective layer,
4...Transfer image receptor.

Claims (1)

[Claims] 1. A recording medium layer containing a non-self-oxidizing binder resin and heat-absorbing fine particles with high light-shielding properties is provided on a transparent support, and a protective layer made of a thermoplastic polymer is further provided on top of the recording medium layer. 1. A laser recording film characterized in that both the recording medium layer and the protective layer contain a heat ray absorber having a strong absorption ability in the wavelength range of the laser light used for recording.