JPS6282083A - Laser recording film - Google Patents

Abstract

PURPOSE:To suppress the increase in the optical density of a laser irradiated part and to dispense with post-treatment and darkroom operation such as development and fixing, by providing a under-coat layer between a transparent support and a recording layer. CONSTITUTION:A under-coat layer 2 is provided on a laser beam permeable support 1 and a layer (recording layer) 3 formed by applying a recording medium containing a non-autoxidizable binder, fine particles imparting high blackening density and absorbing heat and a heat ray absorbent having strong absorbing capacity in the wavelength region of laser beam used in recording is further provided on the under-coat layer 2 and a protective layer 4 comprising a thermoplastic polymer is further provided on the recording layer 3. Recording can be performed by a method wherein laser beam regulated through a usual lens system and a control apparatus is guided while scanned from the side of the support 1 and the recording layer (transfer supply body) 3 and the protective layer 4 are adhered to the image receiving surface of a transfer image receiving body 5 by vapor deposition. The image receiving surface is desirably mounted in contact with the protective layer 4 and, if a close adhesiveness degree is enhanced by pressure reducing operation, resolving power is further bettered.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] 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 removal utilizes the intensity and resolution of the optical energy of the laser beam, and a material with good light absorption is irradiated with L/- laser agitation, and the material absorbed and heated lands on the image receiving surface KZ. It is the iris that attaches to it and records images.

[Conventional technology]

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 (%Kaida No. 48-43632). This recording film is irradiated with a laser beam to transfer particles such as carbon black to the recording tape (by doing so, negative and positive recording is possible.

Also, a binder consisting of a particle that absorbs laser energy, a self-oxidizing binder, and a cross-linkage 41 or a cross-linkable dendrite or a non-oxidizing polymeric substance or resin, or a bond i''+ll. 4 is applied to a transparent film, this is brought into close contact with a lithographic printing surface such as an aluminum notebook, and a laser beam is introduced from the transparent film side to selectively transfer the target material to the lithographic printing surface. A method for manufacturing printing plates has been proposed (Japanese Patent Application Laid-open No.
No. 0-102402). These laser recording films utilize a self-oxidizing binder such as nitrocellulose, and the heat provided 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.

[Problems to be Solved by the Invention] However, as mentioned above, self-oxidizing binders such as nitrocellulose are used as binder resins for the products used in the production of these laser marking films and image-forming printed boards. As a result, they have the disadvantages that acidic substances are generated due to thermal decomposition during image formation and 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 0.5 μm.
Because it was so thin, 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 conducted extensive research to resolve these drawbacks, and have found that a high degree of heating can be achieved by using a non-self-oxidizing binder as the binder and graphite as the heat-absorbing fine particles. Furthermore, by containing a heat ray absorbing agent that has a strong absorption ability in the wavelength range of the YAG laser light used for recording, it is possible to easily transfer the recording medium to the transfer image receiving surface of paper, printing plate, etc. We have discovered that it is possible to obtain a laser recording film that can prevent any residue of the recording medium from remaining on the transparent substrate and that can produce high-resolution negative and positive images.
゛We also discovered that by providing a protective layer made of F and polymer on the surface of the recording layer, it was possible to obtain a laser recording film with remarkable scratch resistance compared to conventional laser recording films. 59-4172
No. 4! ! The application was filed as Fff1 Jyo Sho 59-112311.

However, in this type of laser recording method, especially when the laser output is high, heat generation in the recording layer is significant.
A phenomenon in which the graphite in the recording layer melts onto the surface of the transparent support may be observed. Normally, the recording layer should be transferred to the transfer layer in the area irradiated with the laser, and the optical density of the irradiated area should be the same as that of the transparent support. However, the aforementioned 15! When this phenomenon occurs, the optical power of the part irradiated with the laser increases, and the difference in afw between the part irradiated with the laser light and the part not irradiated with the laser beam decreases, which reduces the performance of the laser recording film as a mask film (light-shielding film).ヰ) is significantly impaired.

[Failure to solve the problem]

The inventors of the present invention have solved these problems, and as a result of careful tax considerations, by providing an undercoat layer between the transparent support and the recording layer, the laser irradiation is faster than with conventional laser recording films. The inventors have discovered a laser recording film that significantly suppresses the increase in optical density of the area, and have arrived at the present invention.

That is, the present invention provides a non-self-oxidizing binder resin on a transparent support provided with an undercoat layer, which provides a high blackening density and absorbs heat, and which has a strong absorption ability in the wavelength region of the laser beam used for recording. The present invention provides a laser recording film which is provided with a recording layer containing a heat ray absorber and further provided with a protective layer made of a thermoplastic polymer thereon.

[Effect]

As shown in FIG. 1, the structure of the laser recording film according to the present invention is as follows: a laser-transmissive support 1 is coated with an undercoat layer 2;
A layer coated with a recording medium that imparts a high blackening density and contains fine particles that absorb heat and a heat ray absorber that has a strong absorption ability in the wavelength range of the laser light used for recording (recording layer)
3. A protective layer 4 made of a thermoplastic polymer is further provided on the recording layer 3.

As shown in Fig. 2, the recording method is to use a normal lens system and adjustment device once again to apply a laser beam to the support 1.
Scanning from the side of 2.4, recording layer (transfer image 1 body) 3
A method can be used in which the protective layer 1 is vapor-deposited in the image-receiving direction of the transfer image-receiving member 5 to record the image f. The image receiving direction is preferably placed in contact with the protective layer 4,
If the density is increased by reducing the pressure, the resolution will be even better.

According to this method, it is possible to simultaneously obtain a blank image on the transfer receiver and a negative f-image on the recording layer 3 in one operation.

Negative film can be used when making printing plates, and Bonn images can be used as proof copies or direct printing plates with 50 types of transfer receivers.

The support for the laser recording film of the present invention may be any film that transmits the laser beam used, such as polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polypropylene, polycarbonate, nylon-6, Examples include films such as ether sulfone. In particular, biaxially stretched films of polypropylene and polyethylene terephthalate are preferred because they have excellent transparency, strength, and dimensional stability.

Graphite and carbon bra are fine particles that absorb heat in the recording layer and achieve a high blackening gradient.

They can be used alone or as a mixture. In particular, finely powdered graphite is suitable for imparting a high blackening density with a light odor.

Examples of the heat ray absorber in the protective layer having a strong absorption ability in the wavelength range of laser light include compounds represented by the following general formula (I) or ffD.

General formula (1) (where R is hydrogen or a lower alkyl group, m is 0 or an integer of 1 or 2.

shows.

Examples of this general formula include bis(p-diethylaminophenyl)CN, N-bis-(p-diethylaminophenyl)-p-7minophenyl]aminium hexafluoroantimonate, hexafluoroarsenate, and peroxide. Chlorate or fluoroborate, N, N, N', N
'-tetrakis(p-diethylaminophenyl)-p-
Hexafluoroantimonate, hexafluoroarsenate, peroxyate or fluoroborate of benzoquinone bisimmonium, bis(p-dipropylaminophenyl)(N,N-bis-(p-dipropylamino) phenyl)-p-aminophenyl]aminium hexafluoroantimonoate, hexafluoroarsenate, perchlorate,
Fluoroborate, N, N, N', N'-tetrakis(p-dipropylaminophenyl)-p-penzoquinone-bisimmonium hexafluoroantimonate, hexafluoroarsenate, perchlorine Acid acid or heptaborate, bis(p-dibutylaminophenyl)
[N,N-bis-(p-'; dibutylaminophenyl-p-aminophenyl]aminium hexafluoroantimonate ion, hexafluoroarsenate, perchlorate, heptaborate, N,N , N', N'-
Tetrakis-(p-dibutylaminophenylfur-benzoquinone bisimmonium) includes hexafluoroantimony d4, hexafluorochloride, perchlorate, fluoroborate, and the like.

(Here, G is hydrogen, an alkyl group, a rogene group, M is nickel, cobalt, palladium, platinum, m is an integer of -1 or -2, and A is a monovalent cation when m is -1) (indicates that m is a divalent cation of −2). Examples of compounds represented by this general formula include bis(1-mercapto-2-naphthlate) nickel (,
l) Tetra-n-butylammonium.

As the non-self-oxidizing binder in the recording layer, acrylic t141]i&, nitrocellulose except cellulose derivatives, phenol phase-resistant, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, etc. can be used.

By using one non-self-oxidizing binder, there are concerns about safety during storage when using self-oxidizing binders such as nitrocellulose, and problems regarding corrosion of the load due to acidic substances generated during laser source irradiation. has completely disappeared.

The blackening density of the recording layer is 0.5 or more, preferably 2.0 or more. If the blackening density is low, the light-shielding performance as a negative film will be poor, and even a positive image will have a weak print.

The amount of the heat ray absorber added is 0.01 to 200 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the non-self-oxidizing binder.
A range of 0 parts by weight is preferred.

The addition of heat and gravel absorbers is especially important for negative films (transfer supply bodies).
It has a strong influence on the transfer of the recording layer, and the solution! ! The effect of raising one ship is significant. When no additive is added, residues tend to remain in the areas removed by the transfer of the recording layer, but this can be almost eliminated, and this is particularly effective when producing negative films for resin plate making.

As the undercoat layer between the recording layer and the transparent support, which is a feature of the present invention, a resin having heat resistance and good transparency can be used.

For example, polycarbonate, polyphenylene sulfide, polyether sulfone, polyarylate, polysulfone, silicone resin, heptan resin, etc. are suitable. An undercoat layer can be formed by dissolving these resins using a suitable solvent, coating and drying using known techniques.

As the thermoplastic polymer used as the protective layer, various mechanically strong polymer substances can be used. For example, vinyl chloride, vinylidene chloride, polycarbonate,
Acrylic m h= such as polystyrene, polymethyl poly(meth)acrylate, cellulose derivatives excluding polyvinyl butyral, polyvinyl alcohol, and cellulose nitrate;
Vinyl polymers and copolymers such as solvent-soluble polyester, solvent-soluble polyamide, vinyl acetate, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, and styrene polymers/copolymers. Polymers, styrene-acrylic copolymers, etc. are preferably used.

When coating a recording layer on an undercoat layer or applying a coating liquid for a protective layer on a recording layer, the liquid dissolves and destroys or changes the recording layer or undercoat layer. Must not be. However, by selecting the coating method and the solvent composition of the coating liquid, stable coating can be achieved even when the recording layer or undercoat layer has no resistance to the solvent. For example, in the case of dipping, fountain reverse method, etc., the protective layer can be coated stably by dissolving the binder of the recording layer.

The thickness of the recording layer and the thickness of the protective layer are influenced by the output of the laser beam used and the amount of heat ray absorber used, but the combined thickness of the recording medium layer and the protective layer is preferably in the range of 0.1 to 2 μm. is preferably 0.2 to 0.5μ. If the protective layer is applied to a thickness sufficient to prevent damage to the recording medium layer, for example, 3 microns or more, the recording layer "W" caused by laser light will be significantly reduced.

The setting of the undercoat (*) between the recording layer and the transparent support in the present invention particularly prevents thermal fusion of graphite in the laser beam irradiated area, and has a remarkable effect of preventing an increase in optical density. By providing an undercoat layer between the transparent support and the recording layer, the optical density of the laser beam irradiated area can be maintained equal to the a degree of the transparent support, improving the performance of the film for racer record e as a mask film. I was able to do that.

Transfer image receptors include general paper, plastic film,
Synthetic paper (white pigment dispersed in plastic film), anodized aluminum, copper-clad dilaminate film, etc. are used.

When using general paper, plastic film, synthetic paper, etc., it can be used as a proof copy or stamp, and when using anodized aluminum, the transferred image can be used as a printing plate by using the mat or rubber lining. When copper-clad laminated film is used, it can be used as an etching protection material for making printed wiring boards.

〔Effect of the invention〕

The laser recording film of the present invention is a real-time recording film that does not require post-processing such as developing and fixing, and is not exposed to light, so darkroom operations are not required. It is ideal for direct recording and can be widely applied.

[Example] The present invention will be described below with reference to Examples. All parts in the examples represent parts by weight.

Example 1 A coating solution consisting of Formulation 1 was applied onto a 100 μm polyester film using a Mayer bar and dried at 50° C. to form an undercoat layer.

A liquid mixture consisting of Formulation 2 was applied onto this by a dip method and dried at 90°C to form a protective layer.

Furthermore, a compounded liquid consisting of formulation 3 was recorded on this recording layer 1-
In the same manner as above, it was applied by the dip method and dried to form a protective layer.

Dry thickness blackening (1 degree earthquake and Nd YAG laser (
Wavelength: 11,064n, output: 1.0W, 0.0W on recording medium.
Table 1 summarizes the results of the imaging test by irradiation (5 Joμle/cyl).

Prescription 1 Silicone face 10 parts (''K
R251' (manufactured by Shin-Etsu Chemical C-) Toluene 10 parts Prescription 2 Graphite 100 parts Ethyl cellulose 36 parts Ethyl acetate
1224 parts bis(p-dimethylaminophenyl) 6
．． 8 parts CN, N-bis-(p-diethylaminophenyl)-p-7 minophenyl] Aminium hexafluoroantimonate formulation 3 Solvent-soluble polyester resin 100 parts (Toyobo (Kiyomi, Byron 200') Methyl ethyl ketone 900 Part Example 2 A coating solution consisting of Formulation 4 was applied onto a 100μ polyester film using a Mayer bar and dried at 100°C to form an undercoat layer.On top of this undercoat layer, Example 1.
A recording layer and a protective layer were provided in the same manner as in .

Dry film thickness, blackening density and Nd YAG laser (
Wavelength 11064n, output 10W, O5J O on recording medium
Table 1 shows the results of the imaging test by irradiation. The trench is shown here.

Formulation 4 Polyarylate 100 parts (1U Polymer U-1060' manufactured by Unitika) Tetrahydrofuran 900 parts Comparative Example A coated film without an undercoat layer on the polyester film in Example 1 was prepared and used as a comparative example.

dryness, thickness, degree of blackening, Nd-YAG laser (wavelength 1
1064n, output 10W, 0.5 Jo on recording medium
ule/ff1) in Table 1. are summarized in

[Brief explanation of drawings]

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 device using the film of the present invention. 1. Support, 2. Undercoat layer, 3. Recording layer, 1.
- Protective layer, 5... Transfer image receptor. Patent Section 1 Person Daicel Chemical Industry Company Representative Patent Attorney Takashi Koshiba Figure 1 Figure 2 Figure 3 Recording Layer

Claims (1)

[Claims] 1 A non-self-oxidizing binder resin on a transparent support,
A recording layer is provided that provides high blackening density and contains heat-absorbing fine particles and a heat ray absorber that has a strong absorption ability in the wavelength range of the laser light used for recording, and a protective layer made of a thermoplastic polymer is provided on top of the recording layer. 1. A laser recording film comprising an undercoat layer between a transparent support and a recording layer.