JPH1134487A - Manufacture of ablation type image forming material and method for forming image by using image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an ablation type image forming material having excellent image durability and no defect, and a method for forming an image suitable to use it. SOLUTION: In the case of forming the ablation type image forming material 4 having a color material layer 2 and protective layer 3 sequentially provided on a transparent support 1 by sequentially coating the support with color material layer forming coating liquid and protective layer forming coating liquid, (1) an evaporating speed V1 of solvent of the material layer forming coating liquid and evaporating speed V2 of solvent of the protective layer forming coating liquid satisfy a relation of 0.15<=V2 /V1 <=1.50, (2) vapor pressure of P1 of the solvent of the material layer forming coating liquid and vapor pressure P2 of the solvent of the protective layer forming coating liquid satisfy a relation of 0.20<=P2 /P1 <=1.50, or (3) surface tension τ1 of the solvent of the material layer forming coating liquid and surface tension τ2 , of the solvent of the protective layer forming coating liquid satisfy a relation of 0.80<=τ2 /τ1 <=1.20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an ablation type image forming material and an image forming method using the image forming material.

[0002]

2. Description of the Related Art Heretofore, a recording method in which light energy such as a laser beam is focused and irradiated onto a recording material to cause a part of the material to be melted, deformed, scattered, burned or evaporated (hereinafter abbreviated). It has been known. These are dry treatments that do not require treatment liquids such as chemicals, and have the advantage that high contrast can be obtained by melting, scattering, or evaporating only the light irradiation part. It is used for optical recording materials such as, for example, and transparent originals at the time of printing plate production.

For example, Japanese Patent Application Laid-Open No. 4-506709, JP-A-6-43635, and US Pat. No. 5,156,938.
Nos. 5,171,650, 5,256,506 and the like, image formation comprising a photothermal conversion material that absorbs laser light and converts it into heat energy and a binder resin that can be decomposed by heat as essential components. Image forming materials having layers are described in JP-A-64-56591, JP-A-1-99887, and
Japanese Patent No. -40163 and the like disclose a material for recording information by removing a colored binder layer by photothermal conversion. Further, U.S. Pat. No. 4,245,003 and the like disclose an image forming layer containing graphite or carbon black. The respective image forming materials are described.

[0004]

With the above-mentioned image forming material, there is a case where a sufficient resolution cannot be obtained or a stain occurs on an image exposed portion. To solve this, Japanese Patent Application Laid-Open Nos. 8-310124, 8-334894, and 8-3
No.37053, No.8-337054, No.8-3370
Nos. 55 and 9-15849 propose image forming materials using ferromagnetic powders as coloring materials, and by using these materials, high-resolution images with less contamination can be obtained.

However, these image forming materials are also
When used for a transparent original at the time of making a printing plate, the durability of the formed image may be poor. Therefore, JP-A-8-337056 discloses that the image surface is protected by a transfer foil or the like after image formation.
No. 95, No. 61-199990, No. 61-20669
Nos. 1, 61-284487 and the like propose providing a protective layer on a color material layer.

In the former, too, waste materials are generated in the former, and in the latter, the color material layer is soft, so that the color material layer is damaged when the protective layer is formed, and the color material layer is eroded by the penetration of the coating solvent. May occur.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a defect-free ablation-type image forming material having excellent image durability and an image forming method suitable for using the same. Is to do.

[0008]

The object of the present invention is to provide an ablation type image forming material having a color material layer and a protective layer in this order on a transparent support, comprising a color material layer forming coating solution and a protective layer forming coating solution. In forming the coating liquid by sequentially applying the coating liquid on the transparent support, the evaporation rate V ₁ of the solvent of the coating liquid for forming the color material layer and the evaporation rate V ₂ of the solvent of the coating liquid for forming the protective layer are 0.25 ≦ V. _Two
A method for producing an ablation-type image-forming material satisfying the relationship of / V ₁ ≦ 1.50, an ablation-type image-forming material having a colorant layer and a protective layer in this order on a transparent support, Upon sequentially applied to formed on the protective layer forming coating solution a transparent support, the vapor pressure P ₂ of the solvent and the vapor pressure P ₁ of the solvent forming the colorant layer coating solution protective layer forming coating solution 0 .20 ≦ P ₂ / P
_A method for producing an ablation-type image-forming material satisfying the relationship of ₁ ≦ 1.50, a method comprising forming a colorant layer-forming coating solution having a colorant layer and a protective layer on a transparent support in this order, by a colorant layer-forming coating liquid and a protective layer. In forming and applying the forming coating liquid sequentially on the transparent support, the surface tension τ ₁ of the solvent of the coating liquid for forming the color material layer and the surface tension τ ₂ of the solvent of the coating liquid for forming the protective layer are 0.80. ≤τ ₂
And a method for producing an ablation-type image-forming material satisfying the relationship of / τ ₁ ≦ 1.20, wherein the value SP ₁ of the solubility parameter of the solvent of the coating material for forming the color material layer and the coating solution for forming the protective layer Solvent solubility parameter value SP ₂ is 0.9
An ablation-type image forming material having a color material layer and a protective layer having a thickness of T on a transparent support in this order, satisfying the relationship of 5 ≦ SP ₂ / SP ₁ ≦ 1.30, is coated with a color material layer forming coating solution. And the protective layer forming coating liquid are sequentially applied on the transparent support to form the coating material. The coating liquid for forming the color material layer has an inorganic oxide having an average particle diameter S that satisfies the relationship of T ≧ 2S. Of an ablation-type image forming material formed by incorporating at least one selected from a material, an inorganic nitride, and an inorganic carbide, and the content of an inorganic oxide, an inorganic nitride, and an inorganic carbide different from the coloring material is a color. 15 of material layer forming component
% By weight or less, individually mixed, and mixed with a colorant-containing liquid and a liquid containing an inorganic oxide, an inorganic nitride, and an inorganic carbide different from the colorant to form a colorant layer-forming coating liquid. Adjusting, after the formation of the protective layer, laminating a release sheet on the protective layer in the manufacturing method of, image exposure with high density energy light from the transparent support side to the image forming material formed by the manufacturing method of The image forming method is performed to remove the exposed portion. The image forming material formed by the manufacturing method is subjected to image exposure with high-density energy light from the transparent support side, and the release sheet is peeled off to expose the color material layer. The image exposure is a scanning exposure using a laser beam, and the wavelength of the laser beam is 600 to 1200 nm.
Is achieved.

Hereinafter, the present invention will be described in detail.

<Production Method of Image Forming Material> The present invention relates to a production method of an ablation type image forming material in which a colorant layer and a protective layer are laminated in this order on a transparent support, and the two layers are coated. It is characterized in that the relationship of the solvent composition at that time is specified, and that the coloring material layer forming composition contains a certain compound other than the coloring material.

As the support, acrylates, methacrylates, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, nylon, aromatic polyamide, polyether Resin films of ether ketone, polysulfone, polyethersulfone, polyimide, polyetherimide, etc., and further, resin films obtained by laminating two or more layers of the above resins can be exemplified.

In the present invention, the support is preferably stretched into a film and heat-set in view of dimensional stability. In the present invention, when performing the image forming method described below,
Since the high-density energy light is imagewise exposed from the support side, a support having a high transmittance to the effective wavelength of the energy light is preferable, and a support having a transmittance of usually 50% or more, more preferably 80% or more is used. Preferably, it is used.

[0013] Fillers such as titanium oxide, zinc oxide, barium sulfate, calcium carbonate and the like may be added as long as the effects of the present invention are not impaired.

The thickness of the support is about 10 to 500 μm,
Preferably it is 25 to 250 μm.

The color material layer can be composed of a color material, a binder resin, and various additives added as required. As the color material, a color material having a color tone according to the intended use can be appropriately selected and used from conventionally known color materials. Further, the color material layer contains a photothermal conversion material having an absorption in a wavelength region of 600 to 1200 nm as other additives in order to efficiently cause ablation in the color material layer by an image forming method described later. Preferably, specifically, cyanine dye, rhodocyanine dye, oxonol dye, carbocyanine dye, dicarbocyanine dye, tricarbocyanine dye, tetracarbocyanine dye, pentacarbocyanine dye, styryl dye, pyrylium dye, phthalocyanine Organic compounds such as dyes and gold-containing dyes, and inorganic compounds such as graphite, carbon black, cobalt trioxide, iron oxide, chromium oxide, copper oxide, titanium black, and magnetic powder can be used. Among these, if the color tone is acceptable, it is preferable to use a material that also functions as a coloring material and a light-to-heat conversion material from the viewpoints of stability and cost of the coating solution during production.

For example, in order to form a black image such as a transparent original at the time of producing a printing plate or a medical diagnostic image, 600-1200 of graphite, carbon black, magnetic powder or the like is used.
A coloring material that absorbs in the wavelength region of nm can be used. In particular, it is preferable to use a magnetic powder from the viewpoint of image resolution and the remaining concentration of the ablation portion. Examples of such magnetic powder include ferromagnetic iron oxide powder, ferromagnetic metal powder, and cubic plate-like powder. Among them, ferromagnetic metal powder can be preferably used.

Examples of the ferromagnetic metal powder include Fe and Co, Fe-Al, Fe-Al-Ni, and Fe-Al-.
Zn-based, Fe-Al-Co-based, Fe-Al-Ca-based, F
e-Ni system, Fe-Ni-Al system, Fe-Ni-Co
System, Fe-Ni-Zn system, Fe-Ni-Mn system, Fe-
Ni-Si system, Fe-Ni-Si-Al-Mn system, Fe
-Ni-Si-Al-Zn system, Fe-Ni-Si-Al
-Co system, Fe-Al-Si system, Fe-Al-Zn system,
Fe-Co-Ni-P system, Fe-Co-Al-Ca system,
Ferromagnetic metal powders such as metal magnetic powders mainly composed of Ni-Co, Fe, Ni, Co, etc.
Base metal powder is preferred.

The shape of the ferromagnetic metal powder is such that the major axis diameter is 0.3.
Needles of 0 μm or less, preferably 0.20 μm or less are preferable. By using such a ferromagnetic metal powder, the surface properties of the coloring material layer can be improved.

The content of the coloring material contained in the coloring material layer is about 50 to 99% by weight, preferably 60 to 99% by weight of the coloring material layer forming component.
95% by weight.

The binder resin for the color material layer can be used without any particular limitation as long as it can sufficiently hold the color material, and may be a polyurethane resin, a polyester resin, a vinyl chloride resin, a polyvinyl acetal resin, Cellulose-based resins, acrylic-based resins, phenoxy resins, polycarbonates, polyamide-based resins, phenolic resins, epoxy resins, and the like can be given.

In order to form a protective layer described later on the color material layer, it is preferable to improve the durability of the color material layer itself. Specifically, after forming the color material layer, the color material layer is cured. Is preferred. Therefore, when an isocyanate-based or carbodiimide-based thermosetting agent is used, as a binder resin, a polyurethane-based resin, a polyester-based resin, a vinyl chloride-based resin, a polyvinyl acetal-based resin, a cellulose-based resin, a phenoxy resin, a polycarbonate, and an acrylic-based resin are used. Those having an active hydrogen group in the molecule, such as a resin, can be appropriately selected and used.

In the case where a ferromagnetic metal powder is used as the coloring material, considering the liquid stability of the coating material for the coloring material layer, -SO ₃ M, -OSO ₃ M, -COO
M and —PO (OM ₁ ) ₂ [where M represents a hydrogen atom or an alkali metal, and M ₁ represents a hydrogen atom, an alkali metal or an alkyl group] It is preferable because the dispersibility of the ferromagnetic metal powder can be improved.

The content of the binder resin is about 1 to 50% by weight, preferably 5 to 60% by weight of the colorant layer forming component.

When a contact-type gravure coater or bar coater is used as a coater for coating the protective layer in the manufacturing method described below, a filler is added to the color material layer for the purpose of preventing the color material layer from being scraped off. Is preferably contained. As the filler, SiO ₂ , TiO ₂ , BaSO ₄ ,
ZnS, MgCO ₃ , CaCO ₃ , ZnO, CuO, Ca
O, WS ₂ , MoS ₂ , MgO, SnO ₂ , Al ₂ O ₃ , α
-Fe ₂ O ₃ , α-FeO ₂ H, SiC, CeO ₂ , Mo
C, BC, WC, BN, SiN, titanium carbide, corundum, artificial diamond, garnet, garnet,
Inorganic compounds such as silica stone, triboli, diatomaceous earth, dolomite, polyethylene resin particles, fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles,
Organic compounds such as melamine resin particles can be exemplified.

Among the above-mentioned fillers, inorganic oxides, inorganic nitrides and inorganic carbides, which are stable to the coating solvent, have a high hardness of the filler itself, and are widely used as abrasives, are more preferred. preferable.

The coloring material layer may further contain additives such as a lubricant, a dispersant and an antistatic agent as long as the effects of the present invention are not impaired.

Examples of the lubricant include fatty acid, fatty acid ester, fatty acid amide, (modified) silicone oil, (modified) silicone resin, fluororesin, carbon fluoride, wax, and the like. Fatty acids having 12 to 18 carbon atoms such as acetic acid and stearic acid and their amides, alkali metal salts, alkaline earth metal salts; polyalkylene oxide alkyl phosphates, lecithin, trialkyl polyolefinoxy quaternary ammonium salts; carboxyl groups And azo compounds having a sulfone group. Examples of the antistatic agent include cationic surfactants, anionic surfactants, nonionic surfactants, polymer antistatic agents, conductive fine particles, and the like, as well as “11290 Chemical Products”, Chemical Daily, p.
And the compounds described in 875-876 and the like. The amount of these additives is from 0 to 0
It is about 20% by weight, preferably 0 to 15% by weight.

The thickness of the color material layer is about 0.05 to 5.0 μm, preferably 0.1 to 3.0 μm. or,
The color material layer may be composed of a single layer or a multilayer having different compositions.

The protective layer can be composed of a binder resin and various additives added as required.

As the binder resin, polyurethane resin, polyester resin, vinyl chloride resin, polyolefin resin, polyvinyl acetal resin, cellulose resin, styrene resin, acrylic resin, polyamide resin, phenol resin, epoxy resin Resins, phenoxy resins, polyvinyl alcohol, gelatin, and the like can be appropriately selected and used, and may be used alone or in combination of two or more. The content of the binder resin in the protective layer is about 10 to 100% by weight, preferably 40 to 100% by weight of the protective layer forming component.

When a binder resin having an active hydrogen group in the molecule is used in order to enhance the durability of the protective layer, an isocyanate compound or a carbodiimide compound or the like may be used in the molecule similarly to the coloring material layer. When a binder resin having the following is used, it is preferable to add a thermosetting agent such as an amine compound.

The protective layer may contain additives such as fillers, lubricants, dispersants, and antistatic agents as long as the effects of the present invention are not impaired. These fillers, lubricants, dispersants, and antistatic agents can be appropriately selected from those added to the above-described coloring material layer and used. The amount of the additive is about 0 to 90% by weight, preferably 0 to 60% by weight of the protective layer forming component.

The thickness of the protective layer is about 0.03 to 2.0 μm, preferably 0.05 to 1.0 μm. The protective layer may be composed of a single layer or multiple layers having different compositions. .

On the back surface of the support of the image forming material, a thickness of 0.0
It may have a backing layer of about 01 to 10 μm.

In the image forming method to be described later, the release sheet provided for peeling off the image after the image exposure is a resin sheet having heat sealing properties, or a resin film used as a support as described above. It may be formed by providing an adhesive layer thereon. The adhesive layer
Any of those that have adhesiveness at room temperature themselves and those that exhibit adhesiveness by applying heat or pressure may be used.For example, a resin having a low softening point, an adhesiveness-imparting agent, a thermal solvent, a filler, and the like may be appropriately selected. Can be formed.

Examples of the resin having a low softening point include polystyrene resin, polyester resin, polyolefin resin, polyvinyl ether resin, acrylic resin, ionomer resin, cellulose resin, epoxy resin, vinyl chloride resin, urethane resin. Examples of the adhesion-imparting agent include unmodified or modified products such as rosin, hydrogenated rosin, rosin maleic acid, polymerized rosin and rosin phenol, terpenes, petroleum resins, and modified products thereof. Further, as the thermal solvent, a known compound which is solid at ordinary temperature and reversibly liquefies or softens when heated can be appropriately selected and used. As the filler, those used for the above-mentioned coloring material layer can be appropriately selected and used.

The thickness of the release sheet is about 6 to 100 μm,
Preferably it is 10 to 50 μm, and the thickness of the adhesive layer is 0.1 μm.
It is about 0.5 to 30 μm, preferably 0.1 to 20 μm.

When coating the colorant layer on the support, the surface may be directly coated, or the surface may be subjected to a corona discharge treatment, if necessary, in order to improve the adhesion to the support and the applicability. It may be modified using a known surface modification technique such as an anchor coat treatment.

The coating material for forming a color material layer and the coating solution for forming a protective layer are prepared by dissolving or kneading and dispersing the above-described components for forming the color material layer and the components for forming the protective layer, respectively, in a solvent.

As the solvent, any solvent having a solubility parameter value in the range of 6.0 to 15.0 shown in "Solvent Pocket Book" edited by The Society of Synthetic Organic Chemistry, Japan, etc. may be used.
Water, alcohols such as ethanol and propanol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as toluene and xylene, ketones such as methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, dioxalan and dioxane And the like, a halogen-based solvent such as chloroform and dichlorobenzene, a nitrogen-containing solvent such as dimethylformamide and N-methylpyrrolidone, and a sulfur-containing solvent such as dimethylsulfoxide.

For kneading and dispersing when a ferromagnetic metal powder is used as a coloring material, for example, a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a cobol mill, a tron mill, a sand mill, a sand grinder, a Sqegvari lighter, a high-speed impeller disperser, A high-speed stone mill, high-speed impact mill, disper, high-speed mixer, homogenizer, ultrasonic disperser, open kneader, continuous kneader, and the like can be used.

In the present invention, by providing the solvent in the coating solution for the color material layer and the protective layer in the following manner, when the protective layer is provided on the color material layer, the adhesion between the layers is ensured. In addition, it is possible to prevent the solvent of the protective layer from excessively penetrating into the color material layer, or to eliminate unevenness in the density of the color material layer caused by non-uniform penetration.

In a first embodiment, the evaporation rate V ₁ of the solvent in the coating liquid for forming the color material layer and the evaporation rate V ₂ of the solvent in the coating liquid for forming the protective layer are 0.25 ≦ V ₂ / V ₁ ≦ 1. Solvent composition that satisfies the relationship of .50. By setting such an evaporation rate, density unevenness of the color material layer can be eliminated, and a high-resolution image can be obtained by an image forming method described later.
In addition, the evaporation rate referred to here is 10 times the evaporation rate of butyl acetate.
The relative evaporation rate per unit volume when it is 0, and when using a mixed solvent, the evaporation rate obtained by the following equation.

Evaporation rate of mixed solvent = Σ (evaporation rate of solvent A × volume of solvent A / total volume of mixed solvent) As a second embodiment, the vapor pressure of the solvent in the colorant layer forming coating liquid is P ₁ , Assuming that the vapor pressure of the solvent of the protective layer forming coating liquid is P ₂ ,
The solvent composition should satisfy the relationship of 0.20 ≦ P ₂ / P ₁ ≦ 1.50. By setting such a vapor pressure, not only repelling unevenness of the protective layer can be prevented, but also a high-resolution image can be obtained by an image forming method described later.
In addition, the vapor pressure referred to here is a value measured at 20 ° C.
When a mixed solvent is used, it refers to the vapor pressure obtained from the following equation.

Vapor pressure of mixed solvent = Σ (vapor pressure of solvent A ×
(Volume of the solvent A / volume of the whole mixed solvent) As a third embodiment, the surface tension of the solvent of the coating material for forming the color material layer is set to τ ₁ , and the surface tension of the solvent of the coating solution for forming the protective layer is set to τ ₂ . The solvent composition is set so as to satisfy the relationship of 80 ≦ τ ₂ / τ ₁ ≦ 1.20. By setting such surface tension,
Not only can cissing unevenness of the protective layer be prevented, but also the residual density of the image exposed portion can be reduced by the image forming method described later. In addition, the surface tension referred to here is a value measured at 20 ° C. When a mixed solvent is used, the surface tension refers to the surface tension obtained from the following equation.

The surface tension of the mixed solvent = Σ (the surface tension of the solvent A × the volume of the solvent A / the total volume of the mixed solvent) In the above three embodiments, the value of the solubility parameter of the solvent in the coating liquid for forming a color material layer is further added. the SP _1, the value of the solubility parameter of the solvent of the protection forming coating solution as SP _2, 0.
By making the solvent composition satisfy the relationship of 95 ≦ SP ₂ / SP ₁ ≦ 1.30, smoothing treatment such as calendering after coating the color material layer or aging after coating the color material layer Thus, the adhesiveness between the heat-cured coloring material layer and the protective layer can be enhanced.

Table 1 shows specific gravity, evaporation rate (V), vapor pressure (P), surface tension (τ), and solubility parameter (SP) values of typical solvents used in the present invention. still,
As the solvent that can be used, a solvent other than those shown in the table can be appropriately selected and used within the scope of the present invention.

[0048]

[Table 1]

The above-described embodiment is a method for reducing the damage of the color material layer at the time of coating the protective layer. Further, the following method also employs a coating method which comes into contact with the color material layer described later. In this case, it is effective because damage to the color material layer can be reduced when the protective layer is applied.

That is, by providing a color material layer formed using a color material layer coating liquid containing at least one of an inorganic oxide, an inorganic nitride, and an inorganic carbide different from the color material, the protective layer is formed. When a coating method that contacts the color material layer during coating is selected, the oxide can prevent the color material layer from being pressed and scraped during coating. As the inorganic oxide, inorganic nitride and inorganic carbide different from these coloring materials, the dried film thickness of the coloring material layer was T, and the average particle diameter of the inorganic oxide, inorganic nitride and inorganic carbide was S. At this time, using a material having a size that satisfies the relationship of T ≧ 2S not only prevents the pressure shaving but also reduces the protrusions on the surface of the color material layer to prevent the coating material from being caught by contact with the coater. The content is preferably not more than 15% by weight of the coloring material layer forming component. Further, to adjust the colorant layer coating liquid containing the inorganic oxide, inorganic nitride and inorganic carbide,
It is preferable that the colorant-containing liquid and the liquid containing the inorganic oxide, the inorganic nitride and the inorganic carbide are individually adjusted and mixed to form a colorant layer coating liquid, and the colorant adjusted by this method is used. When the protective layer coating liquid is applied with a coater that comes into contact with the color material layer that has been applied and dried using the layer coating liquid, pressure shaving can be more effectively prevented.

The reason why the color material layer formed by the above-described method for preparing a color material layer coating solution prevents pressure shaving by a coater in contact is not clear, but inorganic oxides and inorganic nitrides dispersed in a binder resin are not clear. This is probably because substances and inorganic carbides easily emerge on the surface. In addition, separate contained liquids
It can be adjusted by separately dispersing the coloring material, the inorganic oxide, the inorganic nitride and the inorganic carbide in the binder resin dissolving solution by the above-mentioned kneading and dispersing method.

In order to apply a coating solution in which the color material layer forming component and the protective layer forming component are dissolved and / or dispersed, an extrusion type extrusion coater, reverse roll coater, gravure roll coater, air doctor coater, or the like can be used. Various known coater stations such as a blade coater, an air knife coater, a squeeze coater, an impregnation coater, a bar coater, a transfer roll coater, a kiss coater, a cast coater, and a spray coater can be appropriately selected and used. Among these coaters, when applying a color material layer, it is preferable to use a roll coater such as an extrusion-type extrusion coater or a reverse roll coater in order to eliminate thickness unevenness of the color material layer. In addition, when coating the protective layer, there is no particular limitation as long as the color material layer is not damaged, but since the protective layer is thin, in the above-described coater station, Those suitable for thin-layer coating are preferable, and an extrusion-type extrusion coater,
A gravure roll coater, a bar coater or the like can be used. In addition, when using a coating method that contacts the color material layer such as a gravure roll coater or a bar coater, the rotation direction of the gravure roll or the bar may be either forward or reverse with respect to the transport direction, and In the case of forward rotation, a constant speed or a peripheral speed difference may be provided. Furthermore, in the case of using a contacting coating method, it is preferable to perform a smoothing treatment such as a calendar treatment after coating the color material layer, or to use a color material layer coated and then aged and thermoset. Further, it is preferable to use a composition containing an inorganic oxide and / or an inorganic nitride different from the coloring material in the coloring material layer forming composition, since the shaving can be reduced, and thus the composition can be preferably used. .

Incidentally, calendering means that after a color material layer is laminated on a support, temperature and pressure are applied between a highly smooth nip roller, usually 1 cm to 100 cm in diameter, and a heatable roller facing the nip roller. The process is to reduce the voids in the color material layer generated in the application and drying steps of the color material layer coating liquid and to increase the filling rate of the color material layer itself. As conditions for the calendering treatment, it is preferable to apply a nip pressure of usually about 2 to 500 kg / cm, preferably 5 to 300 kg / cm as a linear pressure in order to increase the filling rate of the coloring material layer, The heating temperature is usually 4
The heating temperature is 0 ° C. to 200 ° C., preferably 50 ° C. to 120 ° C. However, since the optimal heating temperature varies depending on the conveying speed, the maximum instantaneous temperature at which the color material layer rises during calendering is usually about 30 ° C. to 100 ° C. It is set as a guide to becoming. The conveying speed is usually 10 to 800 m / min, preferably 30 to 200 m / min.

When the color material layer is aged, the heating temperature when a thermosetting agent is used is usually 30 to 6, depending on the type of curing used and the heat shrinkage of the support used.
The temperature is 5 ° C, preferably 45-60 ° C, and the heating time is usually 24-168 hours, preferably 48-120 hours.

When each layer is coated and dried using the above-described coater station, the time required to enter the drying zone is usually 0.2 to 20 seconds, preferably 0.8 to 1 second.
0 seconds and the time to pass through the drying zone is 0.3-18
0 seconds, preferably 1.5 to 100 seconds. Furthermore, the temperature of the drying zone is usually from room temperature to 120 ° C., preferably from 40 to 100 ° C., depending on how the drying zone is divided, the heat shrinkage of the support, and the tension applied to the support. The air volume is usually 0 to 10000 l / sec, preferably 10 to 5000 l / sec.

When a plurality of types of color material layers are provided, the coating and drying may be repeated for each layer, or may be performed by multi-layer coating by a wet-on-wet method and dried. In that case, a reverse roll coater, gravure roll coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, bar coater, transfer roll coater, kiss coater, cast coater, spray coater, etc. In such multi-layer coating in the wet-on-wet method, the upper layer is coated while the lower layer remains wet, so that the adhesion between the upper and lower layers is improved. I do.

When the release sheet is provided on the protective layer in advance, it can be formed by bonding the protective layer and the release sheet. As a method of laminating the protective layer and the release sheet, when a resin film used for the support is used as the release sheet, if a film having heat sealing properties such as polyethylene or polypropylene is used, the surface of the protective layer may be used. And a film can be laminated and subjected to a heat and pressure treatment using a heat roll or a hot stamp. When using a release sheet provided with an adhesive layer on a resin film such as that used for a support, the protective layer surface and the adhesive layer surface are laminated and bonded by applying heat and pressure using a heat roll or a hot stamp. can do. As a condition for the heat and pressure treatment, when a heat roll is used, the heating temperature is usually room temperature to 180 ° C, preferably 30 to 160 ° C,
The linear pressure is usually 0.1 to 20 kg / cm, preferably 0.5 to 10 kg / cm, and the transport speed is usually 1 to 1 kg / cm.
000 mm / sec, preferably 5 to 500 mm / sec. When using a hot stamp, the heating temperature is from room temperature to 180 ° C, preferably from 30 to 150 ° C, and the pressure is usually from 0.05 to 10 kg / cm ² , preferably from 0.5 to 10 kg / cm ² .
5 kg / cm ² , and the heating and pressurizing time is usually 0.1 to 5
0 second, preferably 0.5 to 20 seconds.

<Image Forming Method> To form an image using the ablation type image forming material manufactured by the above-described manufacturing method, a color material layer 2 is formed on a support 1 as shown in FIG. Using the image forming material 4 in which the layers 3 are sequentially laminated, image exposure with high-density energy light is performed from the support 1 side,
Ablation is caused in the exposed color material layer 2 so that the protective layer surface of the image forming material 4 and the adhesive layer surface of the release sheet 6 having the adhesive layer 5 on the support 1 'as shown in FIG. By facing each other, as shown in FIG. 1 (b), by applying a pressure or heat and pressure, and bonding them, and then peeling off the image forming material 4 and the release sheet 6 as shown in FIG. 1 (c), The exposed portion can be transferred to the release sheet 6 to form an image.

The ablation referred to here means that the color material layer 2 and the protective layer 3 are completely scattered due to a physical or chemical change, a part of the color material layer 2 and the protective layer 3 are destroyed and / or scattered. Or a phenomenon in which only the color material layer 2 is destroyed or a physical or chemical change occurs only in the vicinity of the interface of the color material layer 2 with the support 1.

In image exposure using high-density energy light, any light source capable of causing ablation can be used without any particular limitation. Among them, in order to obtain high resolution, the energy application area is limited. Electromagnetic waves that can be contained, in particular, ultraviolet light, visible light, and infrared light having a wavelength of 1 nm to 1 mm are preferable. Examples of the light source to which such light energy can be applied include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a quartz mercury lamp, a high-pressure mercury lamp, and the like. The energy applied at this time can be appropriately selected and used by adjusting the exposure distance, time, and intensity according to the type of the image forming material.

When laser light is used as a light source,
It is possible to squeeze the light into a beam and perform scanning exposure according to the image data.Furthermore, if a laser is used as a light source, it is easy to narrow the exposure area to a very small size and it is possible to form a high resolution image Become.

As the laser light source used in the present invention, generally well-known ruby lasers, YAG
Laser, glass laser and other solid lasers; He-N
Gas lasers such as e laser, Ar ion laser, Kr ion laser, CO ₂ laser, CO laser, He-Cd laser, N ₂ laser, excimer laser; InGaP laser, AlGaAs laser, Ga
Semiconductor lasers such as AsP laser, InGaAs laser, InAsP laser, CdSnP ₂ laser, and GaSb laser; chemical lasers, dye lasers, and the like; The use of a 1200 nm laser is preferable in terms of sensitivity since light energy can be converted to heat energy.

It is preferable to perform image exposure so that abrasion occurs only at the interface between the support and the colorant layer, since dust and the like do not scatter during image exposure and the image-exposed portion can be transferred uniformly.

As the release sheet 6, a commercially available release sheet, a heat sealing material, a laminate material, or the like can be used as it is, or the above-described release layer provided with an adhesive layer can be used as the release sheet. .

The pressure or heat and pressure treatment with the image forming material and the release sheet facing each other is preferably carried out if the pressure or heat and pressure can be increased without increasing the adhesiveness and without introducing bubbles or the like. Any pressure can be used, and a pressure roll or a stamper can be used for pressurization, and a thermal head, a heat roll, a hot stamp or the like can be used for heat and pressure treatment.

When a pressure roll is used, the pressure is usually preferably 0.1 to 20 kg / cm, more preferably 0.5 to 10 kg / cm, and the conveying speed is usually 0.1 to 1000 mm / sec. preferably, more preferably 0.5～500Mm / sec, the pressure in the case of using the stamper, usually preferably 0.05 to 10 kg / cm ^2, more preferably 0.5 to 5 kg / cm ^2, MataKa The pressure time is usually preferably from 0.1 to 50 seconds, more preferably from 0.5 to 20 seconds. The heating temperature when using a heat roll is usually preferably from 60 to 200 ° C, more preferably from 80 to 180 ° C, and the pressure is usually preferably from 0.1 to 20 kg / cm, more preferably from 0.5 to 20 kg / cm. -10 kg / cm, and the conveying speed is usually preferably 0.1-1000 mm / sec, more preferably 0.5-500 mm / sec, and the heating temperature when using a hot stamp is usually 60 mm / sec. to 200 DEG ° C. are preferred, more preferably in the range of from 80 to 150 ° C., as the pressure, is usually preferably 0.05 to 10 kg / cm ^2, still preferably 0.5 to 5 kg / cm ^2, also the heating time,
Usually, it is preferably 0.1 to 50 seconds, more preferably 0.5 seconds.
~ 20 seconds.

As a method for peeling off, there is no influence on image formation, such as a peeling angle fixing method using a peeling plate or a peeling roll, or a manual peeling method for peeling off a peeling sheet and an image forming material without fixing by hand. Various stripping methods can be used.

In the present invention, whether the image is formed on the image forming material 4 or the image is transferred to the release sheet 6,
It can be used as an image depending on the application. However, when considering high concentration and / or scratch resistance,
It is preferable to use an unexposed portion of the support 1 as an image,
When used as a transparent original, an OHP, a medical image, or the like when creating a printing plate, it is preferable because scratches and the like are not easily formed.

On the other hand, an image can also be formed by the following method.

As shown in FIG. 3A, using the image forming material 4 in which the release sheet 6 is brought into close contact with the image forming material 4 in advance, as shown in FIG. To perform image exposure using high-density energy light to reduce the bonding force between the support 1 and the image forming layer in the exposed portion of the color material layer 2,
By peeling the release sheet 6, the color material layer 2 at the exposed portion
And the protective layer 3 is transferred to the release sheet 6 to form an image.

In this method, in the case of the above-described image forming method, when the image is exposed by high-density energy light, the image forming layer may be scattered depending on the exposure conditions. Since the release layer is provided on the image forming layer of the material, image formation can be performed without such scattering.

In this case, the image forming material 4 and the release sheet 6
May be simply in close contact with each other,
A material in which the image forming material 4 and the release sheet 6 are integrated by lamination can be appropriately selected and used. In the case of using the image forming material 4 and the release sheet 6 which are simply brought into close contact with each other as in the former, the image is formed by exposing the image with high-density energy light, heating and pressurizing, and then peeling the release sheet 6. Can be formed. In the case of the latter, the image can be formed simply by peeling off because it has been pasted in advance, the image forming process is simplified, and the heating and pressing device is not required, so the device can be made compact, More preferred.

A light source of high-density energy light used in an image forming method using a material in which the image forming material 4 and the release sheet 6 are adhered to each other, a pressurizing or heating / pressing method and apparatus, and an image forming material As a method for separating the release sheet 4 from the release sheet 6, a method, an apparatus, or the like used in the above-described image forming method can be appropriately selected and used.

[0074]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the following, “parts” means “parts by weight as active ingredients” unless otherwise specified.

Example 1 The following coloring material layer forming composition was kneaded and dispersed using a Henschel mixer and a sand mill, and then a polyisocyanate compound [Coronate 30 manufactured by Nippon Polyurethane Industry Co., Ltd.]
41; 50% of active ingredient] was added thereto, followed by stirring with a dissolver to prepare a colorant layer forming coating solution.

After the adjusted coating material for forming a color material layer is dispersed in an ultrasonic wave, it is extruded by extrusion and applied to a coating material having a thickness of 1 μm.
A transparent polyethylene terephthalate film (corresponding to one side of 00 μm) treated by corona discharge [Lumirror T6 manufactured by Toray Industries, Inc.
0] on top, dried, then heat roll temperature 90
A calendering treatment was performed at a temperature of 150 ° C., a linear pressure of 150 kg / cm, and a conveying speed of 50 m / sec, and the film was aged at 60 ° C. for 72 hours to form a color material layer having a thickness of 1.0 μm.

(Coloring Material Layer Forming Composition) 100 parts of Fe—Al ferromagnetic metal powder [Fe: Al atomic ratio = 100: 4, average major axis diameter: 0.14 μm] Vinyl chloride resin [Nihon Zeon ( 2. MR-110] 10.0 parts Polyurethane resin [Vylon UR-8200 manufactured by Toyobo Co., Ltd.] 5.0 parts Phosphate ester [Phosphanol RE610 manufactured by Toho Chemical Industry Co., Ltd.] 0 part Solvent 300.0 parts Next, a protective layer forming coating liquid having the following composition was prepared, and after ultrasonic dispersion, extrusion coating by extrusion was used.
After coating and drying on the color material layer,
After aging for a time, a protective layer having a thickness of 0.2 μm was formed.

(Protective Layer Forming Coating Solution) Acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., Dianal BR77) 7.30 parts Silica (manufactured by Fuji Silysia Co., Ltd., Silo Hovic 200) 0.20 parts Polyethylene wax dispersion (Active ingredient: 15% by weight) [Microflat CE-155, manufactured by Koyo Chemical Co., Ltd.] 3.33 parts Carbodiimide group-containing compound [Nippon Shokubai Co., Ltd., Carbodilite V-03] 2.00 parts Solvent 87. 17 parts The solvent composition, evaporation rate, and solubility parameter of each layer used, and the uniformity of concentration of the ablation-type image forming material prepared as described above were evaluated according to the following criteria.

<Uniformity of Concentration> An area of 50 cm × 10 cm, in which a color material layer and a protective layer are provided on a transparent support, has a size of 2.5 cm.
The area was divided into 200 areas of × 1 cm, and the transmission density of each area was measured with a densitometer [X-lite: X-lite].
310TR], and the average density (D _av ) and the density variation (ΔD) at the measurement points were evaluated. Note that the variation in density is ΔD = (maximum density at measurement points−value of minimum density at measurement points).

Next, a semiconductor laser [LT090MD manufactured by Sharp Corporation, main wavelength 830 nm] is applied to each image forming material.
Focus on the interface between the colorant layer and the transparent support,
Image exposure was performed by scanning exposure from the support side, and the surface of the image forming material on the color material layer side and an adhesive tape [Scotch No. 845 book tape] and pressure-adhering treatment (pressure roll, conveyance speed: 30 mm / sec, pressure 3.0 kg / cm) so as to prevent air bubbles from entering, and the image forming material is flattened. Then, the adhesive tape was peeled off (peeling angle 90 °, peeling speed 40 mm / sec), and the image-exposed portion was pulled out to the adhesive tape side to form an image.

The resolution of the formed image and the residual color density of the portion where the color material layer side was transferred to an adhesive tape and removed were evaluated according to the following criteria.

<Resolution> Scanning exposure was performed at a beam diameter of 10 μm, a scanning pitch of 20 μm, and an exposure energy of 300 mJ / cm ² , and the formed image was observed with a microscope, and a resolution per 1 mm at which an image could be formed [N;
/ Mm] was evaluated.

<Remaining concentration> The beam diameter is 10 μm, the scanning pitch is 10 μm, and the exposure energy is 5 at 300 mJ / cm ² .
The scanning exposure is performed so that a solid image of 5 mm × 5 mm is formed, and the transmission density (O
D: measured transmission density−transmission density of the support itself) was measured and evaluated using the visual density of a densitometer [supra].

Table 2 shows the above results.

[0085]

[Table 2]

Example 2 The following colorant layer forming composition was kneaded and dispersed using a Henschel mixer and a sand mill, and then a polyisocyanate compound [Coronate H, manufactured by Nippon Polyurethane Industry Co., Ltd.]
X; 100% of active ingredient] was added thereto, followed by stirring with a dissolver to prepare a colorant layer forming coating solution.

The adjusted coating material for forming a color material layer was dispersed by ultrasonic wave, and then extruded by extrusion to obtain a coating material having a thickness of 1%.
A transparent polyethylene terephthalate film (corresponding to one side of 00 μm) treated by corona discharge [Lumirror T6 manufactured by Toray Industries, Inc.
0], dried and then heated using a heat roll at a temperature of 100 ° C., a linear pressure of 150 kg / cm, and a transport speed of 40 m / m.
A calender treatment was performed in seconds, and aging was performed at 60 ° C. for 72 hours to form a color material layer having a thickness of 0.9 μm.

(Coloring Material Layer Forming Composition) Fe—Si—Al—Ni—Co-based ferromagnetic metal powder [Fe: Si: Al: Ni: Co atomic number ratio = 100: 1: 4: 3: 5, average Long axis diameter: 0.14 μm] 100 parts Polyurethane resin [manufactured by Toyobo Co., Ltd., Byron UR-8200] 15.0 parts Chromium oxide (average particle diameter: 0.13 μm) [manufactured by Nippon Chemical Industry Co., Ltd., U -1] 5.0 parts Phosphate ester [Phosphanol RE610 manufactured by Toho Chemical Industry Co., Ltd.] 3.0 parts Solvent 300.0 parts Then, a protective layer forming coating solution of the following composition was prepared, After the ultrasonic dispersion, the coating was dried on the color material layer by reverse gravure coating and dried, and then aged at 60 ° C. for 72 hours to form a protective layer having a thickness of 0.2 μm.

(Protective Layer Forming Coating Solution) Polyvinyl acetal resin (Eslek BX-55, manufactured by Sekisui Chemical Co., Ltd.) 7.30 parts Silica (Fuji Silysia Co., Ltd., Sylysia 300) 0.20 parts Polyethylene wax Dispersion (active ingredient 15% by weight) [Microflat S-15, manufactured by Koyo Chemical Co., Ltd.] 3.33 parts Carbodiimide group-containing compound [Nippon Shokubai Co., Ltd., carbodilite V-03] 2.00 parts Solvent 187.17 parts The uniformity of the density of the produced ablation-type image forming material was evaluated on the same basis as in Example 1, and the solvent composition, vapor pressure, and solubility parameter of each layer used, and the parameters at the time of forming the protective layer were used. The repelling failure was evaluated according to the following criteria.

<Repelling Failure> A 30 cm × 30 cm area of the prepared ablation-type image forming material was observed with a 40-fold ruler, and a repelling failure having a diameter of 100 μm or more (N)
Was measured.

Separately, a transparent polyethylene terephthalate film (T100E, manufactured by Diafoil Hoechst Co., Ltd.) having a 25 μm single-sided easy treatment was dissolved in a mixed solvent of toluene / methyl ethyl ketone / cyclohexanone = 4/4/2. A polyurethane resin having a solid content of 5% [Nipporan 3109, manufactured by Nippon Polyurethane Industry Co., Ltd.] was applied and dried with a bar coater to provide an adhesive layer having a thickness of 0.45 μm, thereby forming a release sheet.

Next, the protective layer surface of the above-mentioned image forming material and the adhesive layer surface of the release sheet face each other, and are subjected to heat and pressure treatment (roll temperature: 75 ° C., transport speed: 80 mm / sec, pressure: 6.0 kg / cm). Then, an integrated image forming material to which a release sheet was bonded was prepared.

The above-mentioned integrated image forming material was prepared by using a semiconductor laser [LT090MD manufactured by Sharp Corporation, dominant wavelength 830n.
m], the image was exposed by focusing on the interface between the colorant layer and the 100 μm transparent support, and performing scanning exposure from the support side. Next, a 100 μm transparent support was fixed on a flat plate, and the release sheet was peeled off (180 ° peeling angle, 40 mm / sec peeling speed) to pull out the exposed portion to the release sheet side to form an image.

The resolution of the formed image and the residual color density of the exposed portion were evaluated based on the same criteria as in Example 1.

Table 3 shows the above results.

[0096]

[Table 3]

Example 3 The following coloring material layer forming composition was kneaded and dispersed using a Henschel mixer and a sand mill, and then a polyisocyanate compound [Coronate H, manufactured by Nippon Polyurethane Industry Co., Ltd.]
X; 100% of the active ingredient] was added thereto, followed by stirring with a dissolver to prepare a colorant layer forming coating solution.

After the adjusted coating material for forming a color material layer is dispersed in an ultrasonic wave, it is extruded by an extrusion method to a thickness of 1%.
A transparent polyethylene terephthalate film (corresponding to one side of 00 μm) treated by corona discharge [Lumirror T6 manufactured by Toray Industries, Inc.
0], dried and then heated using a heat roll at a temperature of 100 ° C., a linear pressure of 150 kg / cm, and a conveying speed of 60 m / m.
A calendering process was performed in seconds, and aging was performed at 60 ° C. for 72 hours to form a 0.8 μm thick color material layer.

(Coloring Material Layer Forming Composition) 100 parts of Fe—Al ferromagnetic metal powder [Fe: Al atomic ratio = 100: 3, average major axis diameter: 0.16 μm] Polyurethane resin [Toyobo Co., Ltd.] Manufactured by Byron UR-8200] 10.0 parts Polyester resin [manufactured by Toyobo Co., Ltd., Byron 200] 5.0 parts Silicon nitride (average particle diameter: 0.30 μm) [manufactured by Fujimi Abrasives Co., Ltd. GC-5A] 5.0 parts Phosphate ester [Phosphanol RE610 manufactured by Toho Chemical Industry Co., Ltd.] 3.0 parts Solvent 300.0 parts Next, a protective layer forming coating solution having the following composition was prepared. After the ultrasonic dispersion, the solution was applied and dried on the color material layer by forward constant-velocity gravure coating, and then aged at 60 ° C. for 72 hours to form a protective layer having a thickness of 0.15 μm.

(Protective Layer Forming Coating Solution) Phenoxy Resin [PKHH, manufactured by Phenoxy Associates] 7.30 parts Silica [Silohobic 200, manufactured by Fuji Silysia Ltd.] 0.20 parts Polyethylene wax dispersion (active ingredient) [15% by weight] [Microflat S-15, manufactured by Koyo Chemical Co., Ltd.] 3.33 parts Polyisocyanate compound [Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.] 2.00 parts Solvent 187.17 parts Ablation created The uniformity of the density of the mold image forming material was evaluated according to the same standard as in Example 1, and the solvent composition, surface tension and solubility parameter of each layer used, and the repelling failure at the time of forming the protective layer were compared with those of Example 2. Evaluation was made based on the same criteria.

Separately, a transparent polyethylene terephthalate film (T100E, manufactured by Diafoil Hoechst Co., Ltd.) having a thickness of 38 μm which was easily treated on one side was provided with toluene / methyl ethyl ketone / cyclohexanone = 4/4/2.
5% solid content polyurethane resin dissolved in a mixed solvent of Nippon Polyurethane Industry Co., Ltd., Nipporan 311
6] was applied and dried using a bar coater to provide an adhesive layer having a thickness of 0.55 μm, thereby preparing a release sheet.

Next, the protective layer surface of the above-mentioned image forming material and the adhesive layer surface of the release sheet were made to face each other, and subjected to a heat and pressure treatment (roll temperature: 85 ° C., transport speed: 100 mm / sec, pressure: 6.0 kg / cm). Then, an integrated image forming material to which a release sheet was bonded was prepared.

The above-mentioned integrated image forming material was prepared by using a semiconductor laser [LT090MD manufactured by Sharp Corporation;
m], the image was exposed by focusing on the interface between the colorant layer and the transparent support and performing scanning exposure from the support side.

Next, a 100 μm transparent support was fixed on a flat plate, and the release sheet was peeled off (180 ° peeling angle, 40 mm / sec peeling rate), whereby the exposed portion was pulled out to the release sheet side to form an image. The resolution of the formed image and the residual color density of the exposed portion were evaluated based on the same criteria as in Example 1.

Table 4 shows the above results.

[0106]

[Table 4]

Example 4 The procedure of Example 3 was repeated, except that the inorganic particles shown in Table 5 were used instead of silicon nitride in the colorant layer forming composition.
Experiment No. An image forming material was obtained in the same manner as in 3-1.

The uniformity of the concentration was evaluated according to the same criteria as in Example 1, and the repelling failure during the formation of the protective layer was evaluated according to the same criteria as in Example 2.

Using the release sheet prepared in Example 3, an integrated image forming material was prepared under the same conditions, and an image was formed in the same manner.

The resolution of the formed image and the residual color density of the exposed portion were evaluated based on the same criteria as in Example 1.

Table 5 shows the results.

[0112]

[Table 5]

Example 5 The following coloring material layer forming compositions A and B were prepared using a Henschel mixer.
Kneaded and dispersed separately using a sand mill;
Liquid, liquid B and polyisocyanate compound [Nippon Polyurethane Industry Co., Ltd., Coronate HX; active ingredient 100
%] In a weight ratio of 100: 2.39: 0.37,
The mixture was stirred with a dissolver to prepare a colorant layer forming coating liquid.

After the adjusted coating material for forming a color material layer was dispersed in an ultrasonic wave, the thickness of the coating solution was adjusted to 1 by extrusion extrusion.
A transparent polyethylene terephthalate film (corresponding to one side of 00 μm) treated by corona discharge [Lumirror T6 manufactured by Toray Industries, Inc.
0], dried and then heated using a heat roll at a temperature of 100 ° C. and a linear pressure of 150 kg / cm at a conveying speed of 60 m
Per second, and aged at 60 ° C. for 72 hours to form a 0.8 μm thick color material layer.

(Coloring Material Layer Forming Composition) Liquid A Fe—Al ferromagnetic metal powder [Fe: Al atomic ratio = 100: 3, average major axis diameter: 0.16 μm] 100 parts Polyurethane resin [Toyobo Co., Ltd. Co., Ltd., Byron UR-8200] 10.0 parts Polyester resin [Toyobo Co., Ltd., Byron 200] 5.0 parts Phosphate ester [Toho Chemical Industry Co., Ltd., Phosphanol RE610] 3.0 Part Solvent A 300.0 parts Liquid B α-alumina (average particle size: 0.18 μm) [Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 100 parts Polyurethane resin [Toyobo Co., Ltd., Byron UR-8700] 15 parts Phosphate ester [Phosphanol RE610, manufactured by Toho Chemical Industry Co., Ltd.] 3.0 parts Solvent B 118 parts Next, a protective layer forming coating solution having the following composition was prepared, After wave dispersion, the reverse of a bar coater coating, after application and drying on the color material layer, by 72 hours aging at further 60 ° C., to form a protective layer having a thickness of 0.20 [mu] m.

(Protective Layer Forming Coating Solution) Phenoxy resin (PKHH, manufactured by Phenoxy Associates) 7.65 parts Polyethylene wax dispersion (active ingredient: 15% by weight) [Micro flat S-15 manufactured by Koyo Chemical Co., Ltd.] 0.35 parts Polyisocyanate compound (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) 2.0 parts Solvent 200 parts The uniformity of concentration of the prepared ablation-type image forming material was evaluated on the same standard as in Example 1. The flaw failure occurring at the time of applying the bar coater was evaluated according to the following criteria, and the results are shown in Table 6 together with the solvent composition used.

<Scratch Failure> An area of 50 cm × 20 cm of the prepared ablation type image forming material was observed with transmitted light, and the number of transmitted scratches (n) having a length of 5 mm or more was measured.

Separately, an adhesive layer composition having the following composition was applied to an easily accessible surface of a transparent polyethylene terephthalate film (manufactured by Diafoil Hoechst Co., Ltd., T100E) having a thickness of 38 μm, which was easily treated on one side, and dried with a bar coater. Film thickness 1.
An adhesive layer of 30 μm was provided, and a release sheet was prepared.

(Adhesive layer composition) Urethane resin [Nipporan 3109, manufactured by Nippon Polyurethane Industry Co., Ltd.] 4.90 parts Silicone resin particles [Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts Next, the protective layer surface of the above-mentioned image forming material and the adhesive layer surface of the release sheet were made to face each other, and were subjected to a heat and pressure treatment [roll temperature;
0 ° C., transport speed: 80 mm / sec, pressure 6.0 kg / c
m] to form an integrated image forming material on which a release sheet is bonded, and use a YAG laser [DPY521C manufactured by Adras Co., Ltd.]
-NP, output: 4000 mW, main wavelength: 1064 nm], the image was exposed by focusing on the interface between the colorant layer and the transparent support and performing scanning exposure from the support side.

Next, a transparent support having a thickness of 100 μm was fixed on a flat plate, and the release sheet was peeled off (peeling angle: 180 °, peeling speed: 50 mm / sec), whereby the exposed portion was pulled out to the peeling sheet side to form an image. Was.

The resolution of the formed image and the residual color density of the exposed portion were evaluated according to the following criteria.

<Resolution> Scanning exposure was performed at a beam diameter of 10 μm, a scanning pitch of 20 μm, and an exposure energy of 200 mJ / cm ² , and the formed image was observed with a microscope, and a resolution per 1 mm at which an image could be formed [N;
/ Mm] was evaluated.

<Residual density> The beam diameter is 10 μm, the scanning pitch is 10 μm, and the exposure energy is 5 at 200 mJ / cm ² .
A scanning exposure is performed so that an image of 5 mm × 5 mm is formed, and the transmission density (OD: measured transmission density−transmission density of the support itself) of the image-forming material on which the image is formed is measured with a densitometer [X-
The evaluation was carried out using the visual density of X-rite 310TR manufactured by RITE Co., Ltd.].

Table 6 shows the above results.

[0125]

[Table 6]

Example 6 Table 7 was used in place of α-alumina in the coating material B for forming the color material layer.
Experiment No. 1 except that the inorganic oxides, inorganic nitrides, and inorganic carbides shown by No. were used. A coloring material layer and a protective layer were provided in the same manner as in 5-1.

The resolution of the formed image and the residual color density of the exposed portion were the same as those of the fifth embodiment, with the uniformity of the density being the same as that of the first embodiment, and the damage at the time of forming the protective layer being the same as that of the fifth embodiment. Evaluation was made based on the same criteria.

Table 7 shows the results.

[0129]

[Table 7]

[0130]

According to the present invention, even if a protective layer is coated on the image forming layer, the image forming layer is not affected, and the formed image is excellent in durability and has no defects.

[Brief description of the drawings]

FIG. 1 is a view showing one example of an image forming method of the present invention.

FIG. 2 is a view showing a release sheet.

FIG. 3 is a diagram illustrating another image forming method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1, 1 'Support of image forming material and release sheet 2 Color material layer 3 Protective layer 4 Image forming material 5 Adhesive layer 6 Release sheet

Claims (12)

[Claims] An ablation type image forming material having a color material layer and a protective layer in this order on a transparent support is coated with a color material layer forming coating solution and a protective layer forming coating solution sequentially on the transparent support. to form Te, evaporation rate V ₂ of the solvent and the evaporation rate V ₁ of the solvents forming the colorant layer coating solution protective layer forming coating solution 0.
A method for producing an ablation-type image forming material, wherein a relationship of 25 ≦ V ₂ / V ₁ ≦ 1.50 is satisfied. 2. An ablation-type image forming material having a color material layer and a protective layer in this order on a transparent support, and a coating material for forming a color material layer and a coating solution for forming a protective layer are sequentially coated on the transparent support. The vapor pressure P ₁ of the solvent of the coating material for forming the color material layer and the vapor pressure P ₂ of the solvent of the coating solution for forming the protective layer are 0.20 in the formation.
A method for producing an ablation-type image forming material, characterized by satisfying a relationship of ≦ P ₂ / P ₁ ≦ 1.50. 3. An ablation-type image forming material having a color material layer and a protective layer in this order on a transparent support, and a color material layer forming coating solution and a protective layer forming coating solution are sequentially coated on the transparent support. In the formation, the surface tension τ ₁ of the solvent of the coating material for forming the color material layer and the surface tension τ ₂ of the solvent of the coating solution for forming the protective layer are set to 0.
A method for producing an ablation-type image forming material, characterized by satisfying a relationship of 80 ≦ τ ₂ / τ ₁ ≦ 1.20. 4. A value SP ₂ solubility parameter of the solvent and the value SP ₁ of the solubility parameter of the solvent for forming the colorant layer coating solution protective layer forming coating solution _{0.95 ≦ SP 2 / SP 1 ≦} 1.
The method for producing an ablation-type image forming material according to claim 1, wherein the relationship of 30 is satisfied. 5. An ablation type image forming material having a color material layer having a thickness T and a protective layer in this order on a transparent support,
In forming and applying the color material layer forming coating solution and the protective layer forming coating solution sequentially on the transparent support,
An ablation-type image forming material formed by incorporating at least one selected from inorganic oxides, inorganic nitrides, and inorganic carbides different from the coloring material, wherein the average particle diameter S satisfies the relationship of T ≧ 2S. Manufacturing method. 6. The ablation type according to claim 5, wherein the content of the inorganic oxide, inorganic nitride, and inorganic carbide different from the coloring material is 15% by weight or less of the coloring material layer forming component. A method for producing an image forming material. 7. A color material layer forming coating liquid is prepared by mixing individually prepared color material-containing liquids and liquids containing inorganic oxides, inorganic nitrides, and inorganic carbides different from the color materials. 7. The method for producing an ablation-type image forming material according to claim 5, wherein: 8. The method according to claim 1, wherein after forming the protective layer, a release sheet is laminated on the protective layer.
8. The method for producing an ablation-type image forming material according to 5, 6, or 7. 9. An image forming method comprising subjecting an image forming material formed by the manufacturing method according to claim 1 to image exposure with high-density energy light from a transparent support side to remove an exposed portion. . 10. The image forming material formed by the production method according to claim 8 is subjected to image exposure with high-density energy light from the transparent support side, and the exposed portion of the color material layer is peeled by peeling the peeling sheet. An image forming method, wherein the image is transferred onto a sheet. 11. The image forming method according to claim 9, wherein the image exposure is scanning exposure using a laser beam. 12. The laser beam used for image exposure has a wavelength of 600 to 1200 nm.
2. The image forming method according to 1.