JPS62279987A - Laser recording film - Google Patents

Abstract

PURPOSE:To melt a wax by heating by thermal energy, transfer thermal energy generated in a recording layer to a protective layer with a minimum loss and enhance transfer properties, by providing an intermediate layer comprising a specified wax between the recording layer and the protective layer. CONSTITUTION:A recording material comprising a non-autoxidizing binder, a pigment for providing a high blackened density and absorbing heat and a heat ray absorbent having a high absorbing power in the wavelength region of laser light used for recording is applied to a laser light transmitting base 1 to provide a layer (recording layer) 2. An intermediate layer 3 comprising at least one of a paraffin wax, a microcrystalline wax, a polyethylene wax and a carnauba wax is provided on the recording layer 2, and a protective layer 4 comprising a thermoplastic high molecular substance is provided on the intermediate layer 3. When the laser light is directed from the side of the base 1 in a scanning manner and a part of the recording layer (transfer donor) 2 is adhered to an image-receiving surface of a transfer image receiving body 5 through vapor deposition to record an image, a positive image and a negative image can be simultaneously obtained respectively on the image-receiving body 5 and in the recording layer 2 by a single operation.

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 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.

[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 (Japanese Patent Laid-Open No. 48-43632). This recording film enables negative and positive recording by irradiating it with laser light and transferring @ 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 to produce a printing plate 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 Unexamined Patent Publication No. 102402/1982).

All of these laser recording films utilize a self-oxidizing binder such as nitrocellulose, and heat the self-oxidizing binder with the heat provided by the laser light.
It burns or blows out heat-absorbing particles such as carbon black and resin, leaving a blank 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 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 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 made extensive studies to solve these drawbacks, and found that a high blackening density was achieved by using a non-self-oxidizing binder as a binder and further using graphite as 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 beam used for recording, it is possible to easily transfer the recording medium to a transfer image receiving surface such as paper or a printing plate, and it is also transparent. It has been discovered that it is possible to obtain a laser recording film that can prevent the residue of the recording medium from remaining on the substrate and that can give high-resolution negative and positive images. It was discovered that by providing a layer, it was possible to obtain a laser recording film with remarkable #l scratch resistance compared to conventional laser recording films.
No. 4, 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 and causes a problem of decreased recording sensitivity to laser. The scratch resistance is also affected by the material of the protection 1, but generally, as the film thickness increases, the scratch resistance also improves.

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. If a protective layer is provided, when a laser beam is irradiated from the support side, heat attenuation occurs between the recording layer and the protective layer, which may affect transferability and cause a decrease in resolution.

[Means to solve the problem]

The inventors of the present invention conducted extensive studies to solve these problems, and found that paraffin wax, paraffin wax,
By providing an intermediate layer containing at least one type of wax among microcrystalline wax, polyethylene wax, and carnauba wax, we have created a laser recording film that has remarkable image forming properties compared to conventional laser recording films. The present invention was achieved by discovering that the present invention can be obtained.

That is, the present invention consists of a non-self-oxidizing binder resin, a highly light-shielding pigment on a transparent substrate, a heat-absorbing pigment, and a heat ray absorbing agent having a strong absorption ability in the wavelength range of the laser light used for recording. A recording medium layer is provided, and a protective layer made of a thermoplastic polymer is provided on top of the recording medium layer. In a laser recording film, paraffin wax, microcrine wax, or polyethylene wax is used between the recording layer and the protective layer. .

The present invention provides a laser recording film characterized by having an intermediate layer containing at least 11 kinds of carnauba waxes.

[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 heat is applied to the film. A layer (recording layer) 2 coated with a recording medium containing a pigment that absorbs rays and a heat ray absorber that has a strong absorption ability in the wavelength range of the laser beam used for recording, and a layer (recording layer) 2 coated with paraffin.
An intermediate layer 3 containing at least one of wax, microcrystalline wax, polyethylene, wax, and carnauba wax is provided, and a protective layer 4 made of a thermoplastic polymer is further provided on the intermediate layer 3.

As a recording method, as shown in FIG. 2, a laser beam adjusted through a normal lens system and adjustment device is scanned and guided from the side of the support 1, and the recording 11 (transfer supply body) 2 is transferred to the transfer image receiving body 5. 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 4, 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 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 may be any film that transmits laser light, such as polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polypropylene, or polycarbonate.

Examples include films such as nylon-6 and polyethersulfone. In particular, biaxially stretched films of polyethylene terephthalate and polypropylene are preferred because they have excellent transparency, strength, and dimensional stability.

Examples of pigments 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. especially,
Finely powdered graphite is suitable as a material that can provide a high blackening density in a thin film.

Examples of the heat ray absorbent included in the recording material of the present invention include compounds represented by the following general formula (+) or (II).

General formula (1) (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) , m is O or an integer of 1 or 2.

An example of something represented by this general formula (1) is bis(p
-diethylaminophenyl)(N,N-bis-(P-diethylaminophenyl)-p-aminophenyl]aminium hexafluoroantimonate, hexafluoroarsenate perchlorate or fluoroborate, N, N
, N', N'-tetrakis ('P-diethyl 7
Hexafluoroantimonate of sonophenyl-p-benzoquinone-bisimmonium Hexafluoroarsenate Perchlorate or fluoroborate Bis(p-dipropylaminophenyl)(N,N-bis-(p-dipropylamino) Phenyl)-p-7minophenyl 7minium hexafluoroantimonate hexafluoroarsenate perchlorate or fluoroborate N, N,
N', N'-tetrakis(P-dipropylaminophenyl>-p-benzoquinone-bisimmonium hexafluoroantimonate hexafluoroarsenate perchlorate or fluoroborate bis(P-dibutylaminophenyl)(N , N-bis-(P-dibutylaminophenyl)-p-7minophenyl]aminium hexafluoroantimonate hexafluoroarsenate perchlorate or fluoroborate N, N, N'
, N'-tetrakis-(p-dibutyl7minophenyl)-p-benzoquinone-bisimmonium hexafluoroantimonate, hexafluoroarsenate, perchlorate, or fluoroborate.

General formula (ff) (where G is hydrogen, an alkyl group, or a halogen group, M is nickel, cobalt, palladium, or platinum, m is an integer of -1 or -2, and A is one when m is -1). cation, and when m is -2, it indicates a divalent cation.) Examples of compounds represented by this general formula include bis(1-mercapto-2-naphthlate)nickel(t)tetra- There is n-butylammonium.

As the non-self-oxidizing binder in the recording layer, acrylic resins, cellulose derivatives other than nitrocellulose, phenolic resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, etc. 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 or corrosion of equipment due to acidic substances generated during laser light irradiation. lost.

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.

As the thermoplastic polymer used as the protective layer in the present invention, any polymer material with moderate mechanical strength can be used. For example, vinyl chloride, vinylidene chloride, polycarbonate.

Polystyrene, acrylic resins such as poly(meth)methyl acrylate, polyvinyl butyral, polyvinyl alcohol, cellulose derivatives other than cellulose nitrate, solvent-soluble polyesters, solvent-soluble polyamides, vinyl acetate, ethylene-vinyl acetate copolymers , vinyl polymers and copolymers such as ethylene-vinyl acetate-vinyl chloride copolymers, styrene-butadiene copolymers, styrene-
Acrylic copolymers are frequently used.

The amount of heat ray absorber added is 100 parts by weight of non-self-oxidizing binder resin and 100 parts by weight of thermoplastic polymer in each of the recording layer and the protective layer.
α01 to 200 parts by weight, α1 to 1 to parts by weight
A range of 0.00 parts by weight is preferred.

The wax contained in the intermediate layer is preferably paraffin wax, polyethylene wax, microcrystalline wax, or carnauba wax. In order to increase the sensitivity to these wax ponds, the intermediate layer contains the same heat ray absorber or heat absorbing pigment that is added to the recording layer.
For example, graphite, carbon black, etc. can be added. By providing an intermediate layer containing wax between the recording layer and the protective layer, the wax is heated and melted by the thermal energy generated in the recording layer when the laser beam hits it from the transparent substrate side, so that the wax of the present invention can be heated and melted. The setting of the intermediate layer including the recording medium layer made it possible to significantly improve the transferability of the recording medium layer including the recording layer, the 1° intermediate layer, and the protective layer.

When applying a protective layer coating liquid onto the recording layer, the liquid must not dissolve, destroy, or change the recording layer. However, by selecting the coating method and the solvent composition of the coating liquid, it is possible to stably coat the recording material even when the recording material 1 has no resistance to the solvent. For example, in the case of dipping, fountain reverse method, etc., the protective layer can be coated stably using a solvent that dissolves the recording layer.

The thickness of the recording layer, intermediate layer, and protective layer is also affected by the output of the laser beam used and the amount of heat ray absorber added.
The range of α1 to 2μ in total for each layer is good, preferably α2 to
α5μ is good. In particular, the thickness of the intermediate layer is preferably in the range of 0.01 to 0.3μ.

Transfer image receptors include - pattern paper, plastic film,
Synthetic paper (white pigment dispersed in plastic film), anodized aluminum, copper-clad 1@film, etc. are used.

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

〔Effect of the invention〕

An intermediate layer containing at least one type of wax among paraffin wax, microcrystalline wax, polyethylene wax, and carnauba wax between the recording layer and the protective layer for laser recording according to the present invention;
1 was provided because the wax was heated and melted by thermal energy, so that the thermal energy generated in the recording layer could be transmitted to the protective layer with minimal loss, and the transferability could be significantly improved.

〔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), 100μ
,t? It was coated on the J ester film with a Mayano coating 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 110°C to form an intermediate layer. moreover,
In the middle, a liquid mixture consisting of 3 or more formulations was coated on 1 by a dip method, dried at 90°C, and protected.

Formulation 1 Graphite 100 parts Ethylcellulose 36 parts Ethyl acetate 1224 parts Bis(p-diethylamine 13.6 parts Phenyl) (N,N-bis-(p-diethylaminophenyl)-P-aminophenyl) Aminium hexafluoroantimonate formulation 2 Polyethylene wax 100 parts ('A-(Polyethylene 629'' manufactured by Allied Chemical ■) Water 200 parts Prescription 3 Solvent-soluble polyester 100 parts Resin (Pylon 200'' manufactured by Toyobo ■) Methyl ethyl ketone 900 parts Example 2 Example On the recording layer coated in Step 1, a compounded solution consisting of Formulation 4 was applied by a dip method, dried at 110°C, and the intermediate layer was closed. It was coated by the dip method and dried at 90°C to form a protective layer.

Prescription 4 Carnauba wax emulsion 100
Department (1 Parasol BB-30” manufactured by Gokyo Sangyo ■) Water 20
0 parts Prescription 5 Solvent-soluble polyester resin 100 parts (1 Cheminodo 12-1223'' manufactured by Toshi ■) Dioxane
450 parts Microhexanone, 450 parts Example 3 A liquid mixture consisting of Formulation 6 was applied by a dip method onto the recording layer applied in Example 1, and dried at 110'Q to form an intermediate layer. Furthermore, a liquid mixture consisting of Formulation 7 was applied onto this intermediate layer by a dip method and dried at 90°C to form a protective layer.

Prescription 6 +t'rethylene emulsion 1
00 copies (Mitsui Oil Shichigaku ■ 1 Chemipal M-200") Water 300
Part recipe 7 Solvent soluble polyester resin 100 parts (
Good Yaar Co., Ltd. 1 Bityl VPE-100") Dioxane 450 parts THF 450 parts Nd=YAG laser beam collected at 25μ on the recording surface of the laser recording film obtained in the evaluation examples and comparative examples of laser recording film (Wavelength 1064.Q#, output 1o-W.

Recording medium JIQ, 5Jouj! θ/-) was irradiated. The results are shown in Table 1 along with the dry film thickness and blackening density.
It was shown to.

Table 1 Note *1 Blackening density = log('o/E): I
o = Incident light intensity = Transmitted light intensity *2 Using a Nd=YAG laser imaging tester, fine line patterns with 9 different line widths were drawn with a beam diameter of 25 μm.

For each thin line pattern, 1, 2, 3...
A score of 9 was given, and the score of the line width for which the thinnest line width was completely obtained was used as the evaluation.

[Brief explanation of the drawing]

Fig. 1 is a sectional view of a laser recording film of the present invention, and Fig. 2 is a schematic sectional view of a recording device using the film of the present invention. ...Recording layer, 3...Intermediate layer, 4...
- Protective layer, 5... Transfer image receptor. Patent applicant Gwisel Chemical Industry Co., Ltd.
(1 wall with 2 m of dirt)

Claims (1)

[Claims] A recording medium layer consisting of a non-self-oxidizing binder resin, a heat-absorbing pigment that has high light-shielding properties, and a heat ray absorbing agent that has a strong absorption ability in the wavelength range of the laser light used for recording is provided on a transparent substrate. In a laser recording film further provided with a protective layer made of a thermoplastic polymer thereon, at least one of paraffin wax, microcrystalline wax, polyethylene wax, and carnapa wax is used between the recording layer and the protective layer. A laser recording film characterized by having an intermediate layer containing one type of wax.