JPH0725202B2 - Laser recording film - Google Patents

Description

The present invention relates to a laser recording film suitable for recording using a laser beam.

In recent years, many methods using laser light have been proposed in the field where high-speed recording of information or real-time recording is required. This method utilizes the intensity and resolution of the light energy of the laser light, irradiates a substance with good light absorption properties with laser light, absorbs this, and heats the substance to which vapor deposition adheres to the image receiving surface. It records an image.

[Conventional technology]

As this recording film, a recording film coated with fine particles such as carbon black that absorbs heat and a coating material containing a self-oxidizing binding substance such as nitrocellulose has been proposed (JP-A-48-43632). This recording film enables negative and positive recording by irradiating a laser beam to transfer fine particles such as carbon black to another recording tape.

Further, a particle absorbing the laser energy, a self-oxidizing binder and a cross-linking agent or a resin capable of cross-linking or a coating material comprising a non-oxidizing polymer substance or a cross-linking agent combined with a resin is applied to a transparent film, A method for producing a printing plate by bringing this into intimate contact with a lithographic printing surface such as an aluminum sheet and introducing a laser beam from the transparent film side to selectively transfer the coating substance to the lithographic printing surface has been proposed. (JP-A-50-102402). All of these laser recording films utilize a self-oxidizing binder such as nitrocellulose, and the heat supplied by the laser light heats the self-oxidizing binder so that it is burned or ejected to produce a carbon black film. The heat absorbing particles and the resin as described above are carried out to leave a plain area on the film or an image is recorded on the image receiving surface.

[Problems to be solved by the invention]

However, as described above, the binder resin of the material used for the production of these laser recording films and image-forming printed boards contains an auto-oxidizing binder such as nitrocellulose, which causes thermal decomposition during image formation. It has the drawbacks that an acidic substance is generated to corrode the system, there is concern about safety during storage, and the resolution is poor. Furthermore,
The recording layer (recording medium layer) of these laser recording films is easily scratched by itself, and the coating thickness is about 0.5 μm.
Since it was thin, the scratches easily reached not only the surface of the recording layer but also the surface of the substrate.

As a result of diligent studies to eliminate these drawbacks, the present inventors have achieved a high blackening density by using a non-self-oxidizing binder as a binder and by using graphite as fine particles that absorb heat. In addition, a recording medium can be easily transferred to a transfer image-receiving surface of paper, a printing plate, etc. by containing a heat ray absorbent having a strong absorbing ability in the wavelength region of YAG laser light used for recording, and a transparent substrate. It has been found that the residual of the recording medium can be prevented from remaining on the above, and a laser recording film which gives a high-resolution negative and positive image can be obtained,
Further, it was found that by providing a protective layer made of an organic polymer on the surface of the recording layer, a laser recording film having remarkable scratch resistance as compared with the conventional laser recording film was obtained, and the above-mentioned Japanese Patent Application No. 59- No. 41724 and Japanese Patent Application No. 59-112311.

This laser recording film can obtain a high-resolution negative image and a positive image with one exposure of laser light. The film on which the image is recorded can be specifically used for micro film, photomask film, and other high-density recording applications.The image opposite to the image recorded on the film (if the film side is negative, it is a positive image). If the film side is positive, the transfer image receptor on which a negative is recorded can be used as a proof copy or printed matter.

However, when this laser recording film is used as a photomask for exposure of a photosensitive resin plate or a photoresist, in order to increase the resolution, exposure is performed after the coated surface of the film is brought into vacuum contact with the resin plate surface or the resist layer surface, At that time, the coated surface of the film may be soaked by the solvent or the monomer in the resin plate or the resist layer, so that the film cannot be reused as a mask film.

[Means for solving problems]

The inventors of the present invention have conducted extensive studies to eliminate such drawbacks, and as a result, by providing a protective layer having a solvent resistance to a specific solvent made of polyester resin on the surface of the recording layer on the transparent substrate, the conventional laser The present invention has been accomplished by finding that a laser recording film having a significantly improved resistance to a photosensitive composition as compared with a recording film can be obtained.

That is, the present invention comprises a transparent substrate, a non-self-oxidizing binder resin, fine particles for imparting a high blackening density and absorbing heat, and a heat ray absorbent having a strong absorption ability in the wavelength region of the laser beam used for recording. In a film for laser recording provided with a recording layer containing, a protective layer made of a thermoplastic polyester soluble in at least one solvent selected from chlorinated hydrocarbon and cyclic ether is provided on the recording layer. The present invention provides a film for laser recording characterized by the above.

[Action]

As shown in FIG. 1, the structure of the laser recording film according to the present invention is such that a non-self-oxidizing binder, fine particles for imparting a high blackening density and absorbing heat, and a laser used for recording are provided on a substrate transparent to laser light. A layer (recording layer) 2 coated with a recording medium containing a heat ray absorbent having a strong absorption ability in the wavelength region of light, and a protective layer 3 formed of a polyester resin are provided on the recording layer 2.

As a recording method, as shown in FIG. 2, a laser beam adjusted through an ordinary lens system and an adjusting device is scanned and guided from the side of the support 1 to transfer the recording layer (transfer supplier) 2 and the protective layer 3. A method of recording an image by vapor deposition on the image receiving surface of the image receiving body 4 can be used. Image receiving surface is protective layer 3
It is desirable to mount it by contacting it, and if the adhesion is improved by depressurizing operation, the resolution becomes even better.

According to this method, a positive image can be simultaneously formed on the transfer image receptor and a negative image can be simultaneously formed on the recording layer 2 by one operation. The negative film can be used at the time of producing a printing resin printing plate, and the positive image can be used as a proof copy or a direct printing plate depending on the type of the transfer image receptor 4.

The support for the laser recording film of the present invention may be any film that transmits the laser light used, such as polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polypropylene, polycarbonate, nylon-6, polyether sulfone, etc. Film. In particular, biaxially stretched films of polypropylene and polyethylene terephthalate have excellent transparency, strength,
It is preferable because it has excellent dimensional stability.

Examples of the fine particles that absorb heat in the recording layer to achieve a high blackening density include graphite and carbon black, which can be used alone or as a mixture. As a graphite, in order to impart a high blackening density with a thin film,
Usually, fine particles of 2 μm or less are preferable. More preferably, 0.4μ or less is 50% or more, 0.2μ or less is 25
Graphite with a particle size distribution of% or more is suitable.

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

General formula (I) (Here, R is hydrogen or a lower alkyl group, X is an anion selected from the group consisting of a hexafluoroarsenate ion, a hexafluoroantimonate ion, a fluorinated borate ion and a perchlorate ion, and m is 0. Alternatively, it is an integer of 1 or 2.

A is And n is an integer of 1 or 2 and m is 2, A is Indicates. ) Examples of this general formula include bis (p-diethylaminophenyl) [N, N-bis- (p-diethylaminophenyl) -p-aminophenyl] aminium hexafluoroantimonate and hexafluoroarsenic acid. Salt, perchloric acid or borofluoride, N, N, N ', N'-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bisimonium hexafluoroantimonate, hexafluoroarsenate, Oxygenates or fluoroborates, bis (p-dipropylaminophenyl) [N, N-
Bis- (p-dipropylaminophenyl) -p-aminophenyl] aminium hexafluoroantimonate, hexafluoroarsenate, perchlorate, fluoroboronate, N, N, N ', N' -Tetrakis (p-dipropylaminophenyl) -p-benzoquinone-bisimonium hexafluoroantimonate, hexafluoroarsenate,
Perchloric acid or borofluoride, bis (p-dibutylaminophenyl) [N, N-bis- (p-dibutylaminophenyl) -p-aminophenyl] aminium hexafluoroantimonate, hexafluorohydo Acid salt, perchlorate, fluoroboronate, N, N, N ', N'-tetrakis- (p-dibutylaminophenyl) -p-benzoquinone bisimonium hexafluoroantimonate, hexafluoro Examples include arsenate, perchlorate, and fluoroboronate.

General formula (II) (Here, G is hydrogen, an alkyl group, a halogen 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. , And when m is -2, it is a divalent cation.) As an example of the compound represented by this general formula, bis (1-mercapto-2-naphtholate) nickel (II) is shown.
There is tetra-n-butyl ammonium.

As the non-self-oxidizing binder in the recording layer, acrylic resins, cellulose derivatives other than nitrocellulose, phenol resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, etc. can be used. By using a non-self-oxidizing binder, there is no concern about safety during storage when using a self-oxidizing binder such as nitrocellulose, and no problem with equipment corrosion due to acidic substances generated during laser irradiation. Natsuta.

The blackening density of the recording layer is 0.5 or more, preferably 2.0 or more.
When the blackening density is low, the light-shielding performance of the negative film is poor, and a positive image is lightly printed.

The heat ray absorbent is preferably added in an amount of 0.01 to 200 parts by weight, more preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the non-self-oxidizing binder.

The addition of the heat ray absorbent has a great effect on the transfer of the recording layer of the negative film (transfer supplier), and the effect of increasing the resolution is remarkable. In the case of no addition, a residue is liable to remain in the part of the recording layer that has been removed due to the transition, but it can be almost eliminated, and it is particularly effective in the case of preparing a negative film for resin plate making.

It is desirable that the thermoplastic polyester resin of the protective layer material, which is a feature of the present invention, be easily transferred to a transfer image receptor by heat of laser light, but an essential requirement is that it be dissolved in a chlorinated hydrocarbon or a cyclic ether. . Examples include methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2-dibromoethane, tetrachloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, amyl chloride, dichloropentane, monochlorobenzene, 0- Examples include dichlorobenzene, trichlorobenzene, bromobenzene, dioxane, tetrahydrofuran and tetrahydropyran. Solubility of the thermoplastic polyester resin in these solvents, in view of the conditions at the time of coating, at least 100 solvent
It is desirable that 10 parts or more of the resin is uniformly dissolved in each part.

The thermoplastic polyester resin is obtained by using polycarboxylic acid and polyhydric alcohol as raw materials. For example, as the acid component, an aromatic dibasic acid such as terephthalic acid or isophthalic acid, an oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, or the like.
1,2-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
In addition to trimellitic acid, pyromellitic acid and the like, these acid anhydrides, esters, chlorides and the like are used, and ethylene glycol, neopentyl glycol, diethylene glycol, 1,3-propanediol, 1,2 propanediol, 1,2 are used as polyhydric alcohols. -Propane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, triethylene glycol, cyclohexane dimethanol, bisphenol A, hydrogenated bisphenol A There is a polyester resin obtained. Number average molecular weight of polyester resin is 1,000-50,00
The range of 0 is preferable, and 5,000 to 30,000 is preferable.

When the coating liquid for the protective layer is applied onto the recording layer, the liquid must not dissolve the recording layer. However, by selecting the coating method and the solution composition of the coating liquid, stable coating can be performed even when the recording layer has no resistance to the solvent. For example, in the case of the dipping method, the fountain reverse method, the fountain method, etc., the coating can be performed almost stably without affecting the recording layer.

Although 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 the heat ray absorbent used, the range of 0.1 to 2 μ is preferable in accordance with the recording medium layer and the protective layer, and preferably 0.2 to 0.5 μ is good. The thickness of the protective layer is 0.01-0.3μ
Is preferably in the range of 0.05 to 0.15 μ.

As the transfer image receiver, general paper, plastic film,
Synthetic paper (white pigment dispersed in plastic film), anodized aluminum, copper-clad laminated film, etc. are used.

When general paper, plastic film, or synthetic paper is used, it can be used as a proof copy or printed matter.When anodized aluminum is used, the transferred image can be used as it is or as a printing plate with a rubber lining and a copper-clad laminate. When a film is used, it can be used as an etching protective material for making a printed wiring board.

〔Example〕

 The present invention will be described below with reference to examples.

All parts in the examples represent parts by weight.

Preparation of Film for Laser Recording Example 1 A compounded solution consisting of the following formulation 1 was prepared by a dipping method to prepare 100
It was applied to one side of a μ polyester film and dried at 90 ° C. to form a recording layer. A coating solution of Formulation 2 was applied onto this recording layer by a dipping method and dried at 90 ° C. to form a protective layer, thereby obtaining a laser recording film.

Formulation 1 Graphite 100 parts Ethyl cellulose 36 parts Ethyl acetate 1224 parts Bis (p-dibutylaminophenyl) [N, N-bis (p
Hexafluoroantimonate of -dibutylaminophenyl) -p-aminophenylaminium 6.8 parts Formulation 2 Polyester resin 100 parts (Goodyear "Vitel VPE-100") Dioxane 500 parts Cyclohexanone 500 parts Example 2 Implementation A coating solution of Formulation 3 was applied onto the recording layer applied in Example 1 by a dipping method and dried at 90 ° C. to form a protective layer to obtain a laser recording film.

Formulation 3 Polyester resin 100 parts ("Chemitto R-1223" manufactured by Toray Industries, Inc.) Dioxane 500 parts Cyclohexanone 500 parts Example 3 The coating liquid of Formulation 4 was applied onto the recording layer applied in Example 1 by the dipping method, A protective layer was formed by drying at 60 ° C to obtain a laser recording film.

Formulation 4 100 parts of polyester resin ("PES-170" manufactured by Toagosei Kagaku Kogyo Co., Ltd.) 900 parts of methylene chloride Example 4 The coating liquid of Formulation 5 was applied onto the recording layer applied in Example 1 by a dipping method, It was dried at 60 ° C. to form a protective layer to obtain a laser recording film.

Formulation 5 100 parts of polyester resin ("Byron GM460" manufactured by Toyobo Co., Ltd.) 900 parts of methylene chloride Comparative Example 1 The film consisting of only the recording layer coated in Example 1 was used as a comparative example.

Comparative Example 2 On the recording layer applied in Example 1, a coating solution of Formulation 6 was applied by a dipping method and dried at 90 ° C. to form a protective layer.

Formulation 6 Polyester resin 100 parts ("Byron 200" manufactured by Toyobo Co., Ltd.) Toluene 720 parts Methyl ethyl ketone 180 parts Evaluation of laser recording film The laser recording films obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were transparent substrate side. Then, an Nd: YAG laser beam (wavelength 1064 nm, output 10 w, 0.5 joule / cm ² on the recording medium) focused on 25 μm on the recording surface was irradiated. The results are shown in Table 1 together with the dry film thickness of the film and the blackening density.

Next, a repeated durability test of contact exposure of the photosensitive resin plate was conducted using the films to which the images obtained in Examples and Comparative Examples were input. Photosensitive resin plate is NAPP plate GS
(Napsystems Japan) or Niloprint S94 (BASF) was used.

The exposure was performed by bringing the coated surface of the laser recording film and the resin surface of the resin relief plate into close contact with each other, and then exposing for 1 minute with an ultra-high pressure Hg lamp (2 kw) provided at a position 50 cm away from this. After the exposure, the laser recording film was peeled from the resin surface, and the state of the film surface of the film was observed. The results are summarized in Table 2.

[Effect of the invention] The setting of the protective layer made of the polyester resin in the present invention, when the laser recording film is used as a mask film of the photosensitive resin plate, protects the recording layer from the substance contained in the photosensitive resin plate, Durability in repeated exposure using the laser recording film is greatly increased.

[Brief description of drawings]

FIG. 1 is a structural explanatory view showing a specific example of a laser recording film of the present invention, and FIG. 2 is a schematic view showing a state at the time of printing with a laser beam using the laser recording film of the present invention. 1 ... Support, 2 ... Recording layer (transfer supplier), 3 ... Protective layer, 4 ... Transfer image receptor.

Claims (1)

[Claims] 1. A non-self-oxidizing binder resin on a transparent substrate, fine particles for imparting a high blackening density and absorbing heat, and a heat ray absorbent having a strong absorbing ability in the wavelength region of laser light used for recording. In a laser recording film provided with a recording layer containing the recording layer, a protective layer made of a thermoplastic polyester soluble in at least one solvent selected from chlorinated hydrocarbon and cyclic ether is provided on the recording layer. A film for laser recording characterized in that