JPH0447631B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a laser recording film using a heat mode recording method, and more particularly to a laser recording film that has excellent performance as a plate-making film. 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. As this recording film, a recording film coated with a coating material containing heat-absorbing fine particles such as carbon black and a self-oxidizing binding substance such as nitrocellulose has been proposed (Japanese Patent Laid-Open No. 48-43632). 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 and causes 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 of articles used in the manufacture of these laser recording films and image-forming printed boards, so they are susceptible to thermal decomposition during image formation. It has the disadvantages of generating acidic substances that corrode the system, raising concerns about safety during storage, and poor resolution. 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. The present inventors have discovered that it is possible to obtain a laser recording film that can produce high-resolution negative and positive images without leaving any residue, and has arrived at the present invention. That is, the present invention provides a laser recording characterized in that a transparent support is coated with a recording medium containing a non-self-oxidizing binder, graphite, and a heat ray absorber having a strong ability to absorb YAG laser light. The purpose is to provide films for use in As shown in FIG. 1, the structure of the laser recording film according to the present invention is as shown in FIG. It consists of a layer 2 coated with a recording medium containing graphite as fine particles that absorb energy and a heat ray absorber that has a strong absorption ability in the wavelength range of the YAG laser beam used for recording. As a recording method, as shown in FIG. 2, a laser beam 3 adjusted through a normal lens system and adjustment device is scanned and guided from the transparent support 1 side, and a layer (transfer supply body) 2 coated with a recording medium is scanned and guided. A method can be used in which the image is recorded by vapor-depositing it on the image-receiving surface of the transfer image-receiving member 4. It is desirable that the transfer image receiver 4 be mounted in contact with the transfer supply member 2, and resolution can be improved by improving the degree of adhesion by reducing the pressure. According to this method, the transfer image receptor 4 can be transferred in one operation.
A positive image can be obtained on the top and a negative image can be obtained on the transfer supply body 2. The negative film can be used as an original film when producing 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, particularly the laser platemaking film, may be any film that transmits laser light, such as polystyrene film and polyethylene terephthalate film. Graphite, which is used as fine particles to absorb heat in the recording medium and to achieve high blackening density, can be used alone or in a mixture with carbon black or the like. This graphite is preferably in the form of fine particles of usually 2 μm or less in order to provide a high blackening density in a thin film. More preferably, graphite having a particle size distribution in which 50% or more of the particles are 0.4μ or less and 25% or more of the particles are 0.2μ or less is suitable. As a heat ray absorber having a strong absorption ability in the wavelength region of YAG laser light in a recording medium, there are 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

[Formula] is shown. ) Examples of what is shown by this general formula are N,
N,N',N'-tetrakis(p-diethylaminophenyl)-p-aminophenylamium hexafluoroantimonate, hexafluoroarsenate, perchlorate or fluoroborate, N,
N,N',N'-tetrakis(p-dibutylaminophenyl)-p-aminophenylamium hexafluoroantimonate, hexafluoroarsenate, perchlorate or fluoroborate, N ，
N,N',N'-tetrakis(p-diethylaminophenyl)-p-benzoquinone-gisimonium hexafluoroantimonate, hexafluoroarsenate, perchlorate or fluoroborate;
N,N,N',N'-tetrakis(p-dibutylaminophenyl)-p-benzophenone-bisimmonium hexafluoroantimonate, hexafluoroarsenate, perchlorate or fluoroborate, etc. be. General formula; (Here, R ₁ and R ₂ are the same or different alkyl groups, R ₃ is hydrogen, alkyl, phenyl,
benzyl group, m is an integer of +1 or +2, L
is a monovalent anion when m is +1, and m
When is +2, it indicates a divalent anion. An example of a compound represented by this general formula is bis(p-diethylaminophenyl)[N,N-bis(p-diethylaminophenyl)-4'-aminobiphenyl]aminium hexafluoroantimonate. Non-self-oxidizing binders in the recording medium include acrylic resins, cellulose derivatives other than nitrocellulose, phenolic resins, polyvinyl chloride,
Vinyl chloride-vinyl acetate copolymer and the like can be used. By using a non-self-oxidizing binder, there are no concerns about the safety of self-oxidizing binders such as nitrocellulose during storage, and there are no problems with equipment corrosion due to acidic substances generated during laser light irradiation. The blackening density of the recording medium is 0.5 or more, preferably
2.0 or higher. If the blackening density is low, the light-shielding performance as a negative film (original film for plate making) will be poor, and the print will be weak even as a positive image. Therefore, the non-self-oxidizing binder is used in an amount of 20 to 100 parts by weight, preferably 50 parts by weight or less, per 100 parts by weight of graphite. The thickness of the recording medium is influenced by the power of the laser beam used, the blackening density, and the amount of heat ray absorber added, but it is preferably in the range of approximately 0.1 to 1.0 μm, preferably 0.2 to 0.7 μm. If the film thickness is too thick, the resolution will deteriorate or the recording medium will not be transferred.
If the film thickness is too thin, the blackening density will not be reached. The amount of heat ray absorber added, which is a feature of the present invention, is 0.01 to 200 parts by weight per 100 parts by weight of the non-self-oxidizing binder.
Parts by weight, particularly in the range from 0.1 to 100 parts by weight, are preferred. The addition of heat ray absorbers has a great effect on the transfer of recording media, especially negative film (transfer supply material).
The effect of increasing resolution is remarkable. If no heat ray absorber is added, residues tend to remain in the areas where the recording medium is transferred, but this can be almost eliminated by adding a heat ray absorber, and when creating negative film for resin plate making. It is particularly effective for As the transfer image receptor, general paper, plastic film, synthetic paper (white pigment dispersed in plastic film), anodized aluminum, etc. are used. When using ordinary paper, plastic film, synthetic paper, etc., it can be used as a proof copy or printed matter, and when using anodized aluminum, the transferred image can be used as it is or with rubber lining and used as a printing plate. The laser recording film of the present invention is a real-time recording that does not require post-processing such as phenomenon fixation, and since it is not exposed to light, darkroom operation is not necessary, and it can be used for communications and computer processing information that have been rapidly developing in recent years. It is ideal for direct recording and can be widely applied. Hereinafter, the present invention will be explained using examples. All parts in the examples represent parts by weight. Example 1 1.3 parts of Cyasorb IR-126 manufactured by American Cynamid Chemical Co. (hereinafter referred to as ACC) was added as a heat ray absorber to a graphite dispersion consisting of 100 parts of graphite, 30 parts of ethyl cellulose, and 1170 parts of isopropyl alcohol. The added mixed coating liquid was applied onto a polyethylene terephthalate film using a Meyer bar. Table 1 summarizes the dry film thickness, blackening density, and image formation test results by YAG laser (1060 nm; 10 W; 0.5 Joul/cm ² on recording medium) irradiation. In the YAG laser irradiation section, there was no residual recording medium on the transfer supply body, and the image was transferred to the transfer receiver (anodized aluminum plate) with good resolution. Example 2 Instead of the heat ray absorber used in Example 1
The formulation and coating were carried out in the same manner as in Example 1, except that 25 parts of Cyasorb IR-99 (manufactured by ACC) was added. Table 1 summarizes the dry film thickness, blackening density, and image formation test results by YAG laser (1060 nm; 10 W; 0.5 Joul/cm ² on recording medium) irradiation. In the YAG laser irradiation section, there was no residual recording medium on the transfer supply body, and the image was transferred to the transfer image receptor (printed paper) with good resolution. Example 3 Instead of the heat ray absorber used in Example 1
The formulation and coating were carried out in the same manner as in Example 1, except that 5 parts of Cyasorb IR-165 (manufactured by ACC) were added. Table 1 summarizes the dry film thickness, blackening density, and image formation test results by YAG laser (1060 nm; 10 W; 0.5 Joul/cm ² on recording medium) irradiation. In the YAG laser irradiation section, there was no residual recording medium on the transfer supply body, and the image was transferred to the transfer image receptor (printed paper) with good resolution. Example 4 Example 1 except that 1.5 parts of PA-1001 manufactured by Hodogaya Chemical was added instead of the heat ray absorbent used in Example 1.
The same formulation and coating were used. Table 1 summarizes the dry film thickness, blackening density, and image formation test results by YAG laser (1060 nm; 10 W; 0.5 Joul/cm ² on recording medium) irradiation. In the YAG laser irradiation section, there was no residue of the recording medium on the transfer supply body, and the image was transferred to the transfer receiver (anodized aluminum plate) with good resolution. Example 5 A mixture of 1.35 parts of Cyasorb IR-126 as a heat ray absorber added to a graphite dispersion consisting of 100 parts of graphite, 35 parts of phenolic resin, and 540 parts of ethanol was applied using a Meyer bar in the same manner as in Example 1. did. Table 1 summarizes the dry film thickness, blackening density, and image formation test results by YAG laser (1060 nm; 10 W; 0.5 Joul/cm ² on recording medium) irradiation. In the YAG laser irradiation section, there was no residual recording medium on the transfer supply body, and the image was transferred to the transfer image receptor (printed paper) with good resolution. Comparative Example 1 An experiment similar to Example 1 was conducted except that the heat ray absorbent of Example 1 was not added at all. The results are shown in Table 1. In the YAG laser irradiation section, residues of the recording medium remained on the transfer supply body. Comparative Example 2 An experiment similar to Example 5 was conducted except that the heat ray absorbent of Example 5 was not added at all. The results are shown in Table 1. Even when irradiated with YAG laser, the recording medium did not transfer at all.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a laser recording film of the present invention, and FIG. 2 is a schematic cross-sectional view of a recording apparatus using the film of the present invention. 1... Support, 2... Layer coated with recording medium (transfer supply body), 3... Laser light, 4... Transfer image receptor.

Claims (1)

[Claims] 1. A laser recording film comprising a transparent support coated with a recording medium containing a non-self-oxidizing binder, graphite, and a heat ray absorber having a strong ability to absorb YAG laser light.