JPS60255491A - Laser recording film - Google Patents

Abstract

PURPOSE:To provide the titled recording film optimal for the recording of communication and computer processing information with a remarkable resistance to scratching by providing a organic high polymer protective layer on the surface of a recording layer on a transparent substrate while eliminating the need for the operation in a dark room. CONSTITUTION:¦A recording medium which contains (A) a non-self-oxidating binder (e.g. ethylcellulose), (B) fine particles (optimally finely powdered graphite) that gives a high blackening density (preferably, over 2.0) and is able to absorb heat and (C) a heat rays absorbant (optimally, at the rate of 0.1-100pts.wt. per component A) having a strong absorbing power in the wavelength range of a laser light for use in recording are applied on a laser light transmitting support (e.g. polystyrene film) to form a recording layer 2 on which a protective layer 3 made of an organic high molecule (e.g. PVA) is provided to obtain a desired recording film.

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 fields where high-speed or real-time recording of information is required, many methods have been proposed in recent years that utilize laser light.This method utilizes the optical energy and resolution of laser light. A laser beam is irradiated onto a material with good light absorption, and the heated material absorbs the stiffness and is deposited on the image receiving surface to record an image.

[Conventional technology]

As this recording film, a recording film coated with a coating material containing fine particles such as heat-absorbing carbon black and an autooxidizing binding substance such as nitro-hetylulose has been proposed (No. 4, No. 48-45652). ).

This recording film enables negative and positive recording by irradiating it with laser light and transferring fine particles such as carbon black to another recording tape.

Also particles that absorb laser energy.

A coating material consisting of 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 is applied to a transparent film, which is then lithographically printed as an aluminum sheet. A method has been proposed for producing a printing plate by selectively transferring the coating substance to the lithographic printing surface by bringing it into close contact with the surface and introducing a laser beam from the side of the transparent film (Japanese Patent Laid-Open No. 1986-1011).
No. 2402]. All of these laser-grade 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, forming a carbon blank. Transport the heat-absorbing particles and resin.

Do not leave a blank area on the film or leave an image 1'I on the image receiving surface.
This is to record J.

[Problem that the invention seeks to solve]

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 made extensive studies to solve these drawbacks, and found that it was possible to achieve a high blackening density by using a non-self-oxidizing binder as the binder and graphite as the heat-absorbing fine particles. Furthermore, by containing a heat ray absorber that has strong absorption ability in the wavelength range of YA (+ laser light) used for recording, the recording medium can be easily transferred to the transfer image receiving surface of paper, printing plate, etc., and it is transparent. It is possible to prevent any residue of the recording medium from remaining on the substrate.

In addition, a patent application filed in 1983-417 discovered that it was possible to obtain a laser recording film that gave high-resolution negative and positive images.
The application was filed as No. 24.

However, further study revealed that such a recording layer (recording medium layer) itself is easily scratched.

Furthermore, since the dry coating film thickness is as thin as about 0.5 μm, scratches easily reach not only the surface of the recording layer but also the surface of the substrate. Such scratches significantly impair the function of the film for laser bipedal use.

[Means to resolve the problem]

The inventors of the present invention have made extensive studies to overcome these drawbacks, and have decided to provide a protective layer made of organic polymer on the surface of the recording layer on the transparent substrate.

The present inventors have discovered that a laser recording film with remarkable scratch resistance compared to conventional laser recording films can be obtained, and have thus arrived at the present invention.

That is, 1. the present invention comprises, on a transparent substrate, a non-self-oxidizing binder, fine particles that provide high blackening density and absorb heat, and a heat ray absorber that has strong absorption ability in the wavelength range of laser light used for recording. The object of the present invention is to provide a laser recording film provided with a recording layer containing the present invention, which is characterized in that a protective layer made of an organic polymer is provided on the recording layer.

[Effect]

The structure of the laser recording film according to the present invention is as shown in FIG. A layer (recording layer) coated with a recording medium containing: Furthermore, a protective layer 5 made of an organic polymer is provided on the recording layer 2.

As shown in Fig. 2, the recording method is as shown in Figure 2.
A method can be used in which the image is recorded by scanning and guiding from the recording layer (transfer supply body) 2t to the image receiving surface of the transfer image receptor 4 by vapor deposition. It is desirable that the image-receiving surface be in contact with the protective layer 3 for cleaning, and if the degree of adhesion is improved by reducing the pressure, the resolution will be even better.

According to this method, a positive image on the transfer image receptor 4 and a negative image on the recording layer 2 can be simultaneously obtained in one operation. The negative film can be used when making a printing resin printing plate, and the positive image can be used as a proofing film 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 polystyrene film, polyethylene terephthalate film, and the like.

Examples of fine particles that absorb heat in the recording layer and achieve high blackening density include graphite and carbon blank, which can be used alone or as a mixture. In particular, fine powder graphite is preferred as a material capable of imparting a high blackening density in a thin film.

Examples of the heat ray absorber having a strong absorption ability in the laser beam wavelength region in the recording layer include compounds represented by the following general formula (11 or (II)).

General formula (I) (wherein, R is hydrogen or a lower alkyl group, and X is an anion selected from the group consisting of hexafluoroarsenate ion, hexafluoroantimonate ion, fluoroborate ion, and perchlorate ion) 1m is 0 and k is an integer of 1.2.A indicates ÷C or =O=.

N. ,N.

Hexafluoroantimonate of N',N'-tetrakis(p-dibutylaminophenyl)-p-aminophenyl amylam, hexafluorohyde 11m.

Perchlorate or boron fluoride salt, N, N, N-,
NI-tetrakis(p-diethylaminophenyl)-p
- benzoquinone-bisimonium hexafluoroantimonate, hexafluoroarsenate, persodium salt or fluorinated acid salt, N,N.

Examples include hexafluoroantimonate, hexafluoroarsenate, perchlorate, and fluoroborate of Nl, NI-tetrakis(p-dipropylaminophenyl)-p-benzophenone-bisimmonium.

General formula (II) B3 (%R1 and R2 are the same or different alkyl groups t-, R, is hydrogen, alkyl, phenyl, benzyl group, 1m is an integer of +1 or +2, L is m is +1 When , it is a monovalent anion.

Further, when m is +2, it indicates a divalent anion. ) An example of the compound represented by the general formula (II) is bis(p-diethylaminophenyl)(NtN-bis(p-diethylaminophenyl)-4'-7mi/biphenyl)aminium hexafluoroantimonate.

As the non-self-oxidizing binder in the recording layer, acrylic resins, nitrocellulose t-lulose derivatives, phenolic resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, etc. can be used. By using a non-auto-oxidizing binder, there are no concerns about the safety of auto-oxidizing binders such as nitrosylulose 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 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 was 0.01 to 200 M parts per 100 parts by weight of the non-self-oxidizing binder.

Particularly preferred is a range of 0.1 to 100 parts by weight.

The addition of a heat ray absorber has a great effect on the transfer of the recording layer of a negative film (transfer supply body) in particular.

The effect of increasing resolution is remarkable. In the case of no additive, it is easy to leave a residue in the part where the recording layer is transferred, but this can be almost completely eliminated.

This is particularly effective when creating a negative film for resin plate making.

The thickness of the recording layer and the protective layer is affected by the power of the laser beam used, the blackening density, and the amount of heat ray absorber added, but the thickness of the recording layer and the protective layer is 0.1 to 1.0μ in total. The range of (preferably 0.2 to 0.7μ) is good.

When the protective layer is formed to a thickness sufficient to prevent any scratches on the recording layer, for example, approximately 0.5 μm or more, the recording sensitivity by laser is significantly reduced.

Various types of mechanically strong polymer substances can be used as the organic polymer used as the protective layer in the present invention, but when applying the coating liquid for the protective layer on the recording layer, the liquid It must not dissolve or destroy or change. Therefore, the solvents for the coating liquids for the recording layer and the protective layer are limited, and the substances to be coated are also limited.

In the case of a recording layer that is less resistant to solvents.

Water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone, polyacrylic acid, and carboxymethylcellulose.

Aqueous solutions of starch, casein, etc., copolymers of vinyl chloride and vinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyurethane, polyethylene.

A protective layer can be formed by using an aqueous dispersion of carboxylated polyethylene or the like.

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

When using general paper, plastic film, synthetic paper, etc., it can be used as a proof copy or printed matter, and when using entirely anodized aluminum, the transferred image can be used as is.
Alternatively, it can be lined with rubber and used as a printing plate.

〔Effect of the invention〕

The laser recording film of the present invention is a recording film that does not require post-processing such as phenomenon fixing, and is not exposed to light, making it difficult to operate in a dark room. It is ideal for directly recording information and can be widely applied.

〔Example〕

The present invention will be explained below with reference to examples. All parts in the examples represent parts by weight.

Example 1 0yas manufactured by American Cyanamid Chemical Co. was used as a heat ray absorber in the following graphite dispersion (formulation 1).
A blended solution containing 1.5 parts of orb I R-126f was applied onto a 75μ polyester film using a bar code and dried to form a recording layer. A liquid mixture consisting of Formulation 2 was applied onto this recording layer to form a protective layer. Dry film thickness, blackening density, scratch resistance test results, and YA
Table 1 summarizes the results of an image forming test using G laser (wavelength 11060n, output 10W, 0.s above the recording medium, rou1/rs2) irradiation.

Formula 1 Graphite 100 parts Ethyl cellulose 58 parts Inglobil alcohol 1170 parts Formula 2 Polyvinyl alcohol water 96 parts Example 2! J! On the recording layer coated in Example 1, a coating liquid gold consisting of Formulation 5 was applied to form a protective layer. Dry film thickness, blackening density, scratch resistance test results and YAG laser (wavelength 1
1060n, output 10W.

On the recording medium 0.5 JOul/1) 12) [1] The results of the image forming test are summarized in Table 1. - Formulation 5 Acrylic emulsion 5 parts Water 10 parts Example 5 A coating liquid consisting of Formulation 4 was applied onto the recording layer applied in Example 1 to form a protective layer. Dry film thickness, blackening density, scratch resistance test results and YAG laser (wavelength 110
60n, output 10W.

Table 1 summarizes the results of the image forming test using 0.5 Jou1/Plow2) exposure on the recording medium.

Formulation 4 Polyacrylamide 4 parts Water 6 parts Example 4 A coating liquid consisting of Formulation 5 was applied onto the recording layer applied in Example 1 to form a protective layer. Dry film thickness, blackening density, scratch resistance test results, and YAG laser (wavelength 11
060n, output 10W, 0.5 Joul/on recording medium
(To) 2) Table 1 summarizes the results of the image formation test by irradiation.

Formulation 5 Acrylic emulsion 1 part water 10 parts Comparative Example 1 In Example 1, a film coated with only Formulation 1 was used as a comparative example.

(Note*2) The scratch resistance of Examples and Comparative Examples was determined by the following method.

As shown in FIG. 5, support 1. A film consisting of the recording layer 2 and the protective layer 5 was cut into 101) lIXlo- pieces, and 5 ft of paper strips each having a cross-sectional area of 1 sq 2 were placed on the coated surface.

While applying a load of 6, move about 5 am in the horizontal direction.

After that, check whether there are any scratches on the moved part. The test was carried out while changing the load, and the value of the load when the recording layer was scratched was evaluated as the scratch resistance of the protective layer using the following criteria.

The recording layer is not damaged by the load of A Near 50Ji'.

B: The recording layer is not scratched under a load of 5009.

o: The recording layer is scratched by the soy load.

[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. 5 is a diagram showing a measuring method for a scratch resistance test. . DESCRIPTION OF SYMBOLS 1... Support body, 2... Recording layer, 5... Protective layer, 4
...Transfer image receptor. Figure 1 Figure 2

Claims (1)

[Claims] 1. Recording containing, on a transparent substrate, a non-self-oxidizing binder, fine particles that provide high blackening density and absorb heat, and a heat ray absorber that has strong absorption ability in the wavelength range of the laser light used for recording. 1. A laser recording film comprising a layer, characterized in that a protective layer made of an organic polymer is provided on the recording layer.