JP2000006521A - Ablation type image forming material and image forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ablation type image forming material being excellent in the durability of a formed image and resistance to a film cleaner and an image forming method using the same. SOLUTION: An ablation type image forming material which is formed of a metal oxide and which has an image forming layer and a protective layer on a transparent substrate in this sequence, the protective layer being a resin layer prepared by a process wherein a coating solution containing a compound which contains resin having a linkage of wax and urethane in a molecule and can be cured by an activation energy beam is applied on the image forming layer and dried and then hardened by casting the activation energy beam thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ablation type image forming material having high resolution and excellent image durability, and an image forming method using the same.

[0002]

2. Description of the Related Art Conventionally, light energy such as a laser beam is focused to irradiate a recording material to melt, deform, scatter, burn or evaporate a part of the material (hereinafter, these are collectively abbreviated as ablation). A recording method is 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 and deforming only the light irradiation part, scattering or evaporating and removing, and resist materials, It is used as an optical recording material such as an optical disk, a transparent original at the time of producing a printing plate, and the like.

For example, JP-A-8-310124, JP-A-8-310124
No. 334894, No. 8-337053, No. 8-33
No. 7054, No. 8-337055, No. 9-15849
For example, Japanese Patent Application Laid-Open No. H11-163702 proposes an image forming material using a ferromagnetic powder as a coloring material, and by using these image forming materials, a high-resolution image with less contamination can be obtained.

[0004]

However, when the above-described image forming materials are used, there is a case where there is a problem of image durability. In order to solve such problems, for example, Japanese Patent Application Laid-Open No. 2555491, 61-06189
5, No. 61-199990, No. 61-206691
No. 62-234991, JP-A-10-15186
No. 0 and the like propose an image forming material in which a protective layer is laminated on an image forming layer.

[0005] By using such a material, the image durability can be greatly improved. However, when the material is used for a transparent original at the time of making a printing plate, the material may be damaged, or a silver halide film may be used. In some cases, the film cleaner resistance used in the above was inferior.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an ablation type image forming material which is excellent in durability of a formed image and a film cleaner resistance, and an image forming method using the same. is there.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ablation type image forming material having, in this order, an image forming layer and a protective layer containing at least a resin having a urethane bond in a molecule and a wax on a transparent support. Applying a coating liquid containing a resin having a hydroxyl group in the molecule and an isocyanate compound to the image forming layer, and curing after drying to form the resin having the urethane bond in the molecule; In the liquid, the ratio of the isocyanate group equivalent of the isocyanate compound to the hydroxyl equivalent of the resin having a hydroxyl group in the molecule is 1 or more. The image forming layer and the protective layer are provided in this order on a transparent support, and Applying a coating liquid containing a compound curable by an active energy ray onto the image forming layer, and irradiating the protective layer with an active energy ray after drying. An ablation-type image forming material which is a more cured resin layer, wherein the compound curable by the active energy ray is a compound having an unsaturated double bond in the molecule or a compound having an epoxy group in the molecule, transparent An ablation-type image forming material having an image forming layer and a protective layer formed of a metal oxide on a support in this order, wherein the protective layer is formed of inorganic fine particles, organic fine particles, a silicone compound, or a fluorine compound. Wherein the protective layer contains a compound represented by the general formula (1); and a transparent support has an image forming layer and a protective layer in this order, and is transparent. An intermediate layer is laminated between the support and the image forming layer, and the intermediate layer is formed by applying a coating solution containing an isocyanate compound on a transparent support, drying, and then curing. An ablation-type image forming material, which is a resin layer, having an image forming layer and a protective layer on a transparent support in this order, an intermediate layer being laminated between the transparent support and the image forming layer, and the intermediate layer being activated. An ablation-type image forming material that is a resin layer obtained by curing a compound curable by energy rays, having an image forming layer and a protective layer on a transparent support in this order, and an intermediate between the transparent support and the image forming layer. An ablation-type image forming material in which layers are laminated and the intermediate layer is a layer formed of a metal oxide, wherein the image forming layer comprises colorant fine particles and a binder resin; Is a ferromagnetic powder, a release sheet is laminated on a protective layer, and an image is exposed to a laser beam from the transparent support side using an image forming material in which the release sheet is laminated on the protective layer. Was An image forming method for removing and transferring the exposed portions of the image forming layer on the release sheet by peeling the peeling sheet, subjected to image exposure by scanning a laser beam is achieved by.

Hereinafter, the present invention will be described in detail.

In the first embodiment of the present invention, a protective layer laminated on an image forming layer described later has a specific component, such as a resin having a urethane bond in a molecule, an active energy ray. At least one compound selected from the group consisting of resin, metal oxide, wax, inorganic fine particles, organic fine particles, silicone-based compound and fluorine-based compound cured by irradiation, and a compound represented by the general formula (1) And each component is described in detail below.

The resin having a urethane bond in the molecule may be used as a protective layer by previously dissolving the resin having the urethane bond alone in a solvent and coating and drying the resin. It is preferable that a coating liquid containing a resin having a hydrogen group and an isocyanate compound is applied on the image forming layer, dried and cured to form a protective layer containing a resin having a urethane bond.

Examples of such a resin having an active hydrogen group in a molecule include a polyurethane resin, a polyester resin, a polyvinyl acetal resin, a cellulose resin,
Active in the molecule, such as phenoxy resin, epoxy resin, phenol novolak resin, polycarbonate resin, acrylic resin, or modified products of styrene resin, polyolefin resin, vinyl chloride resin, silicone resin, etc. with hydroxyl group or carboxylic acid introduced. A resin having a hydrogen group can be appropriately selected and used. These resins may be used alone or in combination of two or more. If necessary, a resin having no active hydrogen may be used in combination.

Examples of the isocyanate compound include hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4-diphenylmethane diisocyanate, tetramethyl xylylene diisocyanate, and isophorone diisocyanate. , Naphthylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) and the like, and their own polymers and adducts with polyhydric alcohols can be appropriately selected and used. In addition, these isocyanate compounds may be used alone or in combination of two or more.

In order to provide image durability, the ratio of the above-mentioned resin having an active hydrogen group in the molecule to the isocyanate-based compound is defined as the resin having a hydroxyl group in the molecule having an isocyanate equivalent of the isocyanate-based compound. Is preferably 1 or more, more preferably 1.1 or more.

Further, a coating solution containing the above-mentioned resin having an active hydrogen group in a molecule and an isocyanate compound is coated on an image forming layer described later, dried and cured to form a resin layer having a urethane bond. Curing conditions for the heating depend on the type of isocyanate compound used and the heat shrinkage of the support described later, but the heating temperature is usually 30 to 65 ° C, preferably 45 to 60 ° C, and the heating time is Usually 24 to 1
68 hours, preferably 48 to 120 hours.

The durability of an image can also be improved by using a resin cured by irradiation with active energy rays as a protective layer. Such a protective layer is formed by applying a coating liquid containing a compound curable by an active energy ray and an initiator suitable for the active energy ray onto the image forming layer, drying the coating liquid if necessary, and then irradiating the active energy ray. Can be formed.

As the compound which can be cured by an active energy ray, a conventionally known compound having an ethylenically unsaturated double bond or a compound having an epoxy group can be used.

As the compound having an ethylenically unsaturated bond, a known monomer capable of addition polymerization or cross-linking polymerization can be used without particular limitation. Specific examples of the monomer include 2-ethylhexyl acrylate and 2-ethylhexyl acrylate.
Monofunctional acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate and derivatives thereof, or compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, etc .; polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A
Diacrylates, bifunctional acrylates such as diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate and derivatives thereof, or compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, or the like; or trimethylol Polyfunctional acrylates and derivatives thereof, such as propane tri (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and pyrogallol triacrylate, or compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, etc. A so-called prepolymer in which acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to impart photopolymerizability. What is called over it can be used in combination of at least one kind alone or in combination.

The initiator of the compound having an ethylenically unsaturated double bond can be selected depending on the wavelength of the active energy ray. When irradiating with ultraviolet rays, a benzoin compound such as benzoin is used. A carbonyl compound such as Michler's ketone, an azo compound such as azobisisobutyronitrile, a sulfur compound such as dibenzothiazolyl sulfide, a halide such as tribromophenylsulfone, a peroxide such as di-t-butyl peroxide,
Examples include various metal complexes such as iron arene complexes and the like, and if necessary, a sensitizing dye suitable for ultraviolet rays may be added.

As the compound having an epoxy group in the molecule, a known crosslinkable compound having an epoxy group can be used without any particular limitation. Specific compounds include polycondensates of bisphenol A and epichlorohydrin, polycondensates of hydrogenated bisphenol A and epichlorohydrin, polycondensates of brominated bisphenol A and epichlorohydrin, polycondensates of bisphenol F and epichlorohydrin, Glycidyl-modified phenol novolak,
Glycidyl-modified o-cresol novolak, aliphatic polyglycidyl ether, polyglycol glycidyl ether, monoglycidyl ether, tertiary carboxylic acid monoglycidyl ether, and the like can be used alone or in combination of two or more. Can be.

When ultraviolet light is used as an active energy ray as an initiator for a compound having an epoxy group in the molecule, an amine compound (eg, ammonia, ethylenediamine, diethylenetriamine, phenylenediamine, etc.)
(III) complex having an amine compound as a ligand or a compound capable of generating a Bronsted acid (hereinafter referred to as an acid generator). Acid generators capable of causing a reaction are more preferred.

Such acid generators include 2,4,6-
S-triazine compounds substituted with trihalomethyl groups such as tris (trichloromethyl) -1,3,5-triazine, [η6-i-propylbenzene], [η5-cyclopentadienyl] iron hexafluorophosphate, etc. Iron arene complexes, onium salts such as diphenyliodonium hexafluorophosphate, aryldiazonium salts, diazoketones, o-nitrobenzyl esters,
Examples include sulfonic acid esters, disulfone derivatives, imidosulfonate derivatives, silanol-aluminum complexes, and the like.

The active energy ray-curable compound is used in an amount of about 1 to 90% by weight, preferably 5 to 70% by weight of the protective layer forming component, and the initiator is an active energy ray-curable compound. Usually 0.1 for 100 parts by weight
It is preferably used in the range of 100 to 100 parts by weight, more preferably 0.5 to 50 parts by weight.

In addition to the compound curable by the active energy ray, a resin not involved in curing may be used in combination, if necessary. Further, in the present invention, an active energy ray-cured product which is commercially available in which a compound curable by an active energy ray and an initiator are mixed in advance, can be appropriately selected and used in the present invention.

As the active energy ray, any light source capable of activating the initiator can be used without particular limitation.
When ultraviolet light is used as the effective active energy ray of the initiator, light sources such as sunlight, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, and a xenon lamp are appropriately selected. Can be used. Here, the ultraviolet light means light in the ultraviolet region, and also includes light rays including light in the ultraviolet region.

Atmosphere when irradiating ultraviolet rays is as follows:
An inert gas atmosphere such as air, nitrogen gas or carbon dioxide gas is preferred.

The irradiation time of the ultraviolet rays varies depending on the type of the compound curable by the active energy ray, the initiator and the light source, but is usually 0.5 seconds to 5 minutes, preferably 3 seconds to 2 minutes. Usually, when the irradiation time is short, a large light source with a large irradiation intensity is required, and when the irradiation time is long, a light source with a small irradiation intensity can be used.

At the time of curing, when the protective layer film is heated before or after the irradiation of ultraviolet rays, the curing time can be shortened. When such heating is performed, the heating temperature is preferably 30 to 80 ° C. Before ultraviolet irradiation, the heating time at the heating temperature may be longer or shorter, but after ultraviolet irradiation, the heating time is preferably 1 minute to 120 minutes.

Further, the image durability can be improved by forming a protective layer made of a metal oxide. The protective layer made of a metal oxide is formed by applying and drying a coating liquid containing an organic metal compound or an inorganic compound and an acid or a catalyst such as an alkali to cause hydrolysis and condensation polymerization of the organic metal compound or the inorganic compound. Can be formed.

As the organometallic compound or inorganic compound, silicon, zirconium, titanium, aluminum, boron,
Germanium, lithium, sodium, iron, gallium,
Metal alkoxides such as magnesium, phosphorus, antimony, tin, tantalum, and vanadium; metal acetylacetonates such as aluminum and titanium; metal oxalates such as K ₂ TiO (C ₂ O ₄ ) ₂ ; metal nitrates such as aluminum and zirconium ,
Al ₂ (SO ₄ ) ₃ , (NH ₄ ) Al (SO ₄ ) ₂ , KAl
Metal sulfates such as (SO ₄ ) ₂ and NaAl (SO ₄ ) ₂ , metal oxychlorides such as silicon and zirconium, and chlorides such as aluminum, silicon, zirconium and titanium can be mentioned. These organometallic compounds or inorganic compounds may be used alone or in combination of two or more.

Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as acetic acid, fluoroacetic acid, p-toluenesulfonic acid, diphenyl phosphate and picric acid; alkali metals and alkaline earth metals. And amine compounds such as ethanolamine and triethanolamine. These catalysts may be used alone or in combination of two or more kinds. The amount of the catalyst added is 0.001 to the organometallic compound or the inorganic compound.
-10% by weight is preferred.

Further, a coating liquid containing an organic metal compound or an inorganic compound for forming a protective layer made of a metal oxide and a catalyst such as an acid or an alkali may be used in order to initiate a reaction. Preferably, 0.05 to 50 mol of water is added to the compound, and for the purpose of adjusting flexibility and slipperiness, if necessary, polyvinyl alcohol, polyvinyl acetate, or the above-mentioned urethane bond in the molecule. A resin having an active hydrogen group in the molecule used for forming the resin having the same or a resin having an amino group in the molecule such as polyamide may be added. The content of these resins is preferably 200% by weight or less based on the amount of the organic metal compound or the amount of the inorganic compound.

In the present invention, other additives may be added to the protective layer in order to further improve image durability, and the additives include wax, inorganic fine particles, organic fine particles, silicone compound, and fluorine compound. By adding at least one compound selected from the above at the appropriate time, especially the scratch resistance of the image durability can be improved.

When a resin having a urethane bond in the molecule is used as the above-mentioned protective layer, a wax is contained as an essential component in order to improve the scratch resistance.

The above-mentioned wax, inorganic fine particles and organic fine particles are preferably added in a state where they are previously dispersed in a coating solution, and the average particle diameter of the dispersion is not more than 20 times the thickness of the protective layer. Is preferable from the viewpoint of retaining fine particles.

Examples of the wax include polyolefin-based wax, paraffin-based wax, vegetable wax, animal wax and the like, and inorganic fine particles such as SiO ₂ , Ti
O ₂ , BaSO ₄ , ZnS, MgCO ₃ , CaCO ₃ , Zn
O, CuO, CaO, WS ₂ , MoS ₂ , MgO, SnO
₂ , Al ₂ O ₃ , α-Fe ₂ O ₃ , α-FeO ₂ H, SiC,
CeO ₂ , MoC, BC, WC, BN, SiN, titanium carbide, corundum, artificial diamond, garnet, garnet, silica stone, triboli, diatomaceous earth, dolomite, etc., and as the organic fine particles, polyethylene resin particles, fluorine Resin particles, guanamine resin particles,
Acrylic resin particles, silicon resin particles, melamine resin particles and the like can be mentioned. Examples of the silicone-based compound include dimethylpolysiloxane, methylphenylpolysiloxane and modified products obtained by graft-polymerizing or block-polymerizing the same with another resin, and examples of the fluorine-based compound include polytetrafluoroethylene resin particles and polytrifluoroethylene. Resin particles such as ethylene resin particles, and hydrocarbons, fluorine-substituted carboxylic acids, sulfonic acids, phosphoric acids, and derivatives thereof, are exemplified.

The amount of these additives is 70% by weight or less, preferably 50% by weight or less in the composition for forming a protective layer.

Further, in the present invention, particularly low-speed scratch resistance in image durability can be further improved by further adding the compound represented by the general formula (1).

The thickness of the above protective layer is usually 0.05 to 5.
0 μm, preferably 0.15 to 3.0 μm. or,
The protective layer may be composed of a single layer or a multilayer having different compositions.

In forming the above protective layer, the solvent for dissolving or kneading and dispersing the components of the protective layer may be any solvent having a solubility parameter in the range of 6.0 to 15.0. Alcohols such as 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, and ethers such as dioxalan and dioxane And halogen-based solvents such as chloroform and dichlorobenzene, nitrogen-containing solvents such as dimethylformamide and N-methylpyrrolidone, and sulfur-containing solvents such as dimethylsulfoxide.

When kneading and dispersion are required, 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,
Sqegvari Attritor, High Speed Impeller Disperser, High Speed Stone Mill, High Speed Impact Mill, Disper,
A high-speed mixer, a homogenizer, an ultrasonic disperser, an open kneader, a continuous kneader or the like can be appropriately selected and used.

In order to apply a coating liquid in which the prepared protective layer forming component is dissolved and / or dispersed, an extrusion type extrusion coater, reverse roll coater, gravure roll coater, air doctor coater, blade coater, air knife, etc. Coater, squeeze coater,
Various known coater stations such as an impregnating 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, the coating of the protective layer is not particularly limited as long as the image forming layer is not damaged, but when the thickness of the protective layer is small, the coating in the above-described coater station is performed. Preferably, a material suitable for thin-layer coating is used, 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 such as a gravure roll coater or a bar coater that contacts the image forming layer, 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, when using a contacting coating method, an image forming layer to be described below is subjected to a smoothing treatment such as a calendar treatment after coating, or an image forming layer is coated and then cured and heat-cured. Is preferred.

Another embodiment of the present invention is characterized in that an intermediate layer composed of a specific component is provided between an image forming layer described later and the support, and the support and the image are provided by installing the intermediate layer. While improving the adhesive strength with the formation layer,
It is possible to reduce the contamination of the exposed portion, which cannot be achieved by the intermediate layer formed of another resin layer or the like.

Specific examples of the intermediate layer in the present invention include a layer formed by applying a coating solution containing an isocyanate compound on a transparent support, drying and curing the coating.

This layer may be used alone with the isocyanate compound used for forming the resin having a urethane bond used in the above-mentioned protective layer, or may be used in combination with a resin having an active hydrogen group in the molecule. When a resin is used in combination, 80% or less of the composition for forming an intermediate layer, preferably 60% or less.
% Is preferred.

The transparent support on which the coating solution containing the isocyanate compound is applied is preferably subjected to a corona discharge treatment from the viewpoint of the film.

The intermediate layer in the present invention may completely react the isocyanate group in the isocyanate-based compound, or may be partially unreacted for the purpose of improving the adhesion with the image forming layer described later. good.

The same effect can be obtained by using a layer made of a resin or a metal oxide cured by irradiating the active energy ray used in the protective layer described above for the intermediate layer.

The thickness of the intermediate layer of the present invention is usually from 0.001 to
It is 1.0 μm, preferably 0.005 to 0.5 μm. The intermediate layer can be provided in the same manner as the protective layer.

The transparent support used in the image forming material of the present invention includes acrylates, methacrylates, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, Resin films such as polystyrene, nylon, aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, and polyetherimide, and further, resin films obtained by laminating two or more layers of the resin can be used. .

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 laser light is exposed imagewise from the support side, a support having a high transmittance for the effective wavelength of the energy light is preferable, and a support having a transmittance of usually 50% or more, and more preferably 80% or more is used. Is preferred. Incidentally, titanium oxide, zinc oxide, barium sulfate, as long as the effects of the present invention are not impaired,
A filler such as calcium carbonate may be added.

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

The image forming layer can be composed of fine particles, a binder resin and various additives added as required.

As the fine particles in the image forming layer, fine particles having a color tone corresponding to the intended use can be appropriately selected from fine particles which can be conventionally known coloring materials (hereinafter abbreviated as coloring material fine particles). it can.

The above-mentioned coloring material fine particles are more preferable from the viewpoint of the stability of the coating liquid at the time of production and the cost, in which the laser light is efficiently converted into heat to cause ablation. For example, to create a black image such as a transparent manuscript or medical diagnostic image when creating a printing plate, graphite, carbon black, metal nitride, metal carbide, metal boride, cobalt tetroxide, iron oxide, Chromium oxide, copper oxide,
600-1200nm for titanium black, magnetic powder, etc.
Colorant particles that absorb in the wavelength range of
In particular, it is more preferable to use a magnetic powder from the viewpoint of image resolution and residual density in a portion where ablation has occurred.

Such magnetic powders include ferromagnetic iron oxide powder,
Ferromagnetic metal powder, cubic plate-like powder and the like can be mentioned, and among them, ferromagnetic metal powder can be suitably used.

Examples of such ferromagnetic metal powders include F
e, Co, Fe-Al-based, Fe-Al-Ni-based,
Fe-Al-Zn system, Fe-Al-Co system, Fe-Al
-Ca-based, Fe-Ni-based, Fe-Ni-Al-based, Fe-
Ni-Co system, Fe-Ni-Zn system, Fe-Ni-Mn
System, Fe-Ni-Si system, Fe-Ni-Si-Al-M
n-based, Fe-Ni-Si-Al-Zn-based, Fe-Ni-
Si-Al-Co system, Fe-Al-Si system, Fe-Al
-Zn system, Fe-Co-Ni-P system, Fe-Co-Al
-Ca-based, Ni-Co-based, Fe, Ni, ferromagnetic metal powders such as metal magnetic powders whose main component is Co, and the like,
Among them, Fe-based metal powder is preferable.

The shape of the ferromagnetic metal powder is preferably acicular with a major axis diameter of 0.30 μm or less, preferably 0.20 μm or less. By using such a ferromagnetic metal powder, the surface of the image forming layer can be formed. Performance can be improved. The content of the coloring material fine particles is 50% of the components for forming the image forming layer.
About 99% by weight, preferably 60 to 95% by weight.

The binder resin for the image forming layer can be used without any particular limitation as long as it can sufficiently retain the coloring material fine particles.

Examples of such a binder resin include polyurethane resins, polyester resins, vinyl chloride resins, polyvinyl acetal resins, cellulose resins,
Acrylic resin, phenoxy resin, polycarbonate,
Examples thereof include a polyamide resin, a phenol resin, and an epoxy resin.

In order to form the protective layer on the image forming layer, it is preferable to improve the durability of the image forming layer itself. Specifically, after forming the image forming layer, the image forming layer is cured. Is preferred.

When the image forming layer is cured as described above, an isocyanate-based or carbodiimide-based thermosetting agent can be used. As the binder resin used at this time, a polyurethane-based resin, a polyester-based resin,
Active in the molecule used when forming a resin layer having a urethane bond in the molecule in the protective layer, such as a vinyl chloride resin, a polyvinyl acetal resin, a cellulose resin, a phenoxy resin, a polycarbonate, and an acrylic resin. A resin having a hydrogen group can be appropriately selected and used.

When ferromagnetic metal powder is used as the coloring material fine particles, considering the liquid stability of the coating solution for the image forming layer, -SO ₃ M and -OSO _{3 are} contained in the binder resin.
At least one selected from M, —COOM 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 to have a kind of polar group since 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 components for forming the image forming layer.

When a contact-type gravure coater or bar coater is used as a coater for coating the protective layer, the image forming layer is provided with a protective layer other than the coloring material fine particles in order to prevent the image forming layer from being scraped off. Inorganic fine particles added to the
It is preferable to contain organic fine particles, fine particles such as fluorine-based compounds, among which inorganic particles, inorganic oxides and inorganic oxides widely used as abrasives, which are stable to the coating solvent and have high hardness of the fine particles themselves Nitride and inorganic carbide are more preferred.

For the purpose of reducing projections on the surface of the image forming layer, the content of such inorganic oxides, inorganic nitrides and inorganic carbides should be 15% by weight or less in the image forming layer forming composition. Is preferred.

In the image forming layer, in addition to the above-mentioned coloring material fine particles, a binder resin and, if necessary, a thermosetting agent and fine particles, a light-to-heat conversion compound and a lubricant, as long as the effects of the present invention are not impaired. And additives such as a dispersant and an antistatic agent.

The light-to-heat conversion compound is added to the image forming layer in addition to the above-mentioned coloring material fine particles to improve the heat conversion efficiency of the laser light. Known dyes such as cyanine dyes, oxonol dyes, carbocyanine dyes, dicarbocyanine dyes, tricarbocyanine dyes, tetracarbocyanine dyes, pentacarbocyanine dyes, styryl dyes, pyrylium dyes, phthalocyanine dyes, and gold-containing dyes Can be.

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 a cationic surfactant, an anionic surfactant, a nonionic surfactant, a polymer antistatic agent, and conductive fine particles.

The amount of these additives is about 0 to 20% by weight, preferably 0 to 15% by weight of the components for forming the image forming layer.
It is.

In the present invention, the thickness of the image forming layer is set to 0.1.
About 05 to 5.0 μm, preferably 0.1 to 3.0 μm
Range. Further, the image forming layer may be composed of a single layer or a multilayer having different compositions.

In the image forming method to be described later, a release sheet provided for peeling off an image by irradiating with a laser beam is used as a release sheet made of a heat-sealing resin sheet or as a transparent support as described above. It may be formed by providing an adhesive layer on a resin film. The adhesive layer may be any of those having adhesiveness at normal temperature per se and those exhibiting adhesiveness by applying heat or pressure, for example, a resin having a low softening point, an adhesiveness-imparting agent, a hot solvent, a wax, and fine particles. It can be formed by appropriately selecting the above.

Examples of the resin having a low softening point include polystyrene resins, polyester resins, polyolefin resins, polyvinyl ether resins, acrylic resins, ionomer resins, cellulose resins, epoxy resins, vinyl chloride resins, and urethane resins. 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 wax and the fine particles, those used for the above-mentioned protective 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 a release sheet provided with an adhesive layer is used, the release sheet can be provided on a release sheet support in the same manner as the protective layer.

As a method for bonding the protective layer and the release sheet, when a resin film such as that used for a transparent support is used as a release sheet, any film having heat sealing properties such as polyethylene or polypropylene may be used. For example, lamination can be performed by laminating the protective layer surface and the film and subjecting them to 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 transparent support,
Lamination can be performed by laminating the protective layer surface and the adhesive layer surface and performing heat and pressure treatment using a heat roll or a hot stamp. The conditions for the heat and pressure treatment are as follows:
When a heat roll is used, the heating temperature is usually room temperature to 180 ° C, preferably 30 to 160 ° C, and the linear pressure is usually 0.1 to 20 kg / cm, preferably 0.1 kg / cm.
5-10 kg / cm, and the transport speed is usually 1-100
0 mm / sec, preferably 5 to 500 mm / sec.
When a hot stamp is used, the heating temperature is between room temperature and 1
80 ° C., preferably 30 to 150 ° C., and the pressure is usually 0.05 to 10 kg / cm ² , preferably 0.5 to 5 k
g / cm ² , and the heating and pressurizing time is usually 0.1 to 50.
Seconds, preferably 0.5 to 20 seconds.

Further, in the image forming material of the present invention, other layers may be provided in addition to the transparent support, the intermediate layer, the image forming layer, the protective layer, and the release sheet. A backing layer on the side of the transparent support opposite to the image forming layer and / or the side opposite to the image forming layer of the release sheet for the purpose of preventing blocking, and a protective layer between the image forming layer and the protective layer. A sealing layer may be provided for the purpose of preventing the penetration of the coating solvent.

<Image Forming Method> The image forming material of the present invention is obtained by irradiating light from the transparent support side imagewise.
An image can be formed on the transparent support by causing ablation in the exposed portion and then peeling off the release sheet. In addition, any light source can be used without particular limitation as long as it can generate ablation.
By using laser light, it is possible to stop in a beam shape and perform scanning exposure according to 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 high resolution Since an image can be formed, it can be suitably used.

The image exposure with a laser beam can be used without any particular limitation as long as it is a light source which ablates at the interface between the transparent support and the image forming layer. Electromagnetic waves whose energy application area can be narrowed down, in particular, ultraviolet rays, visible rays, and infrared rays having a wavelength of 1 nm to 1 mm are preferable. As such laser light sources, generally known ruby lasers and YAGs
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.

In the case of scanning exposure, either the outer surface scanning or the inner surface scanning may be performed depending on the power of the laser light source or the like. Or with an intermediate layer,
Either exposure method may be used as long as it causes ablation at the interface with the image forming layer, but exposure is preferably performed from the transparent support side from the viewpoint of energy efficiency.

The ablation referred to here means that the image forming layer and the protective layer are completely scattered by a physical or chemical change, a part of the image forming layer and the protective layer are destroyed and / or scattered. This includes a phenomenon in which only the formation layer is destroyed and a physical or chemical change occurs only near the interface between the image formation layer and the transparent support or the intermediate layer.

Examples of a method of peeling the exposed image forming material include a peeling plate, a method of fixing a peeling angle with a peeling roll, and a manual peeling method of peeling off the peeling sheet and the image forming material without fixing the image forming material by hand. Various peeling methods can be used as long as they do not affect the peeling.

[0082]

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 image forming layer forming compositions were separately kneaded and dispersed using a Henschel mixer and a sand mill.
Liquid, two liquids 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 an image forming layer forming coating solution.

The prepared coating solution for forming an image forming layer was ultrasonically dispersed, and then extrusion-coated by an extrusion method, and a transparent polyethylene terephthalate film having a thickness of 100 μm and having one surface subjected to corona discharge treatment [Lumilar T60, manufactured by Toray Industries, Inc.] Coating and drying, then using a heat roll, temperature 100 ° C, linear pressure 150 kg / cm, transport speed 6
A calendar process is performed at 0 m / sec.
After aging for 0 hour, an image forming layer having a thickness of 0.80 μm was formed.

<Image Forming Layer Forming Composition> One-part ferromagnetic metal powder [MAP T1650SB manufactured by Kanto Denka Kogyo KK] 100 parts Polyurethane resin [Byron UR4122 manufactured by Toyobo Co., Ltd.] 13.5 parts Phenoxy resin [Phenoxy resin PKHH, manufactured by Phenoxy Associates] 1.5 parts Phosphate ester [Phosphanol RE610, manufactured by Toho Chemical Industry Co., Ltd.] 3.0 parts Methyl ethyl ketone 105.0 parts Toluene 105.0 parts Cyclohexanone 90.0 parts 2 parts Alumina [manufactured by Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 100 parts Polyurethane resin [manufactured by Toyobo Co., Ltd., Byron UR4122] 15 parts Methyl ethyl ketone 41.3 parts Toluene 41.3 parts Cyclohexanone 35.4 parts Coating solution for forming protective layer having the following composition 1-5 Beauty 14,
15 (for comparison) was adjusted using a sand mill, and after ultrasonic dispersion, coated on the image forming layer by a reverse bar coater and dried, and then aged at 60 ° C. for 72 hours. A protective layer having the thickness described was formed.

<Protective Layer Forming Coating Solution 1> Phenoxy resin [Phenoxy Associates, Phenoxy resin PKHH] 3.0 parts Polyester resin [Elitel UE3690, manufactured by Unitika Ltd.] 3.65 parts Polyethylene wax dispersion (effective (15% by weight of component) [Microflat CE-155, manufactured by Koyo Chemical Co., Ltd.] 2.33 parts Polyisocyanate compound [Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.] 3.0 parts Toluene 120.0 parts Cyclohexanone 80 0.0 parts <Protective layer forming coating liquid 2> Phenoxy resin [Phenoxy resin PKHH manufactured by Phenoxy Associates, Inc.] 2.0 parts Polyester resin [Elitel UE3690 manufactured by Unitika Ltd.] 3.8 parts Silicone resin [Dainichisei Chemical Co., Ltd., Dialomer SP2105] 1.0 part Ethylene wax dispersion (active ingredient 15% by weight) [Koyo Chemical Co., Ltd., Microflat CE-155] 1.33 parts Polyisocyanate compound [Nippon Polyurethane Industry Co., Ltd., Coronate HX] 3.0 parts Toluene 120.0 parts Cyclohexanone 80.0 parts <Coating liquid for forming protective layer 3> Polyurethane resin [manufactured by Toyobo Co., Ltd., Byron UR4122] 3.0 parts Polyester resin [manufactured by Unitika Ltd., Elitel UE3690] 3.0 Part Alumina [High purity alumina HIT60G, manufactured by Sumitomo Chemical Co., Ltd.] 0.8 part Polyethylene wax dispersion (15% by weight of active ingredient) [Koyo Chemical Co., Ltd., Microflat CE-155] 1.33 parts Poly Isocyanate compound [Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.] 3.0 parts Toluene 120. 0 parts Cyclohexanone 80.0 parts <Protective layer forming coating liquid 4> Phenoxy resin [Phenoxy resin PKHH, manufactured by Phenoxy Associates] 2.0 parts Polyester resin [Toyobo Co., Ltd., Byron PCR926] 5.0 parts Polyethylene Wax dispersion (active ingredient 15% by weight) [Microflat CE-155 manufactured by Koyo Chemical Co., Ltd.] 3.33 parts Silica [Silohobic 200 manufactured by Fuji Silysia Chemical Ltd.] 0.2 parts Stearic acid 0.3 parts Polyisocyanate compound [Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.] 2.0 parts Toluene 120.0 parts Cyclohexanone 80.0 parts <Coating liquid 5 for forming protective layer> Polyester resin [Toyobo Co., Ltd.] 6.5 parts Silicone modified resin [manufactured by Toa Gosei Chemical Industry Co., Ltd. Imac US270] 1.5 parts Polyethylene wax dispersion (15% by weight of active ingredient) [Koyo Chemical Co., Ltd., Microflat CE-155] 3.33 parts Silica [Fuji Silysia Chemical Ltd., Silo Hobik] 200] 0.2 parts Stearic acid 0.3 parts Polyisocyanate compound [Nippon Polyurethane Industry Co., Ltd., Coronate HX] 1.0 parts Toluene 90.0 parts Methyl ethyl ketone 90.0 parts Cyclohexanone 20.0 parts <Protective layer formation Coating liquid 14> Polyester resin [manufactured by Toyobo Co., Ltd., Byron 200] 10.0 parts Toluene 120.0 parts Cyclohexanone 80.0 parts <Coating liquid 15 for forming protective layer> Polyester resin [manufactured by Toyobo Co., Ltd.] , Byron 290] 10.0 parts Dichloroethane 200.0 parts Separately 38 μm thick single-sided easy treatment The transparent polyethylene terephthalate film [Diafoil Hoechst Co., T100E] the easy contact surface of the coating an adhesive layer composition of the following composition in a bar coater, dried film thickness of 1.30μm
Was provided to produce a release sheet.

<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 Then, 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 heated and pressurized [roll temperature;
0 ° C. (80 ° C. for protective layers 14 and 15), transport speed: 80
mm / sec, pressure 6.0 kg / cm] to produce an integrated image forming material having a release sheet bonded thereto.

Using the image forming material produced in this manner, the focal point is adjusted to the interface between the transparent support of the image forming material and the image forming layer, and the EV laser proofer [PS data] is used using postscript data (PS data). Konica Corporation,
After exposing at a rotation speed of 425 and a power of 100%], the film was peeled off, and the resolution, stains on the exposed portion, scratch resistance and film cleaner resistance were evaluated according to the following criteria. In addition,
The halftone dot% in the evaluation standard is shown by the halftone dot% of the unexposed portion.

-Evaluation of Resolution- An image is formed using a vertical stripe pattern in the main scanning direction of the drum of 2000 DPI as PS data, and the formed vertical stripe pattern is arbitrarily extracted at 30 points in the main scanning direction, and the loupe is used in the sub scanning direction. And evaluated the average number of lines / spaces per inch (this is regarded as one) and the difference between the maximum number and the minimum number (Δ number).

-Evaluation of dirt on the exposed portion- A 0% halftone image was formed at a screen ruling of 175 lines, a halftone dot square, and a screen angle of 45 °, and the transmission density of the formed halftone image was adjusted to an arbitrary 30%. The point is measured with a densitometer [Xr
It was measured using the visual density of X-rite 310TR manufactured by ITE, and the average density ODav was evaluated.

◎: Average density is less than 0.050 ○: Average density difference is 0.050 or more and less than 0.060 Δ: Average density difference is 0.060 or more and less than 0.075 ×: Average density difference is 0.075 or more .

Evaluation of Scratch Resistance- A 50% halftone image is formed at a screen ruling of 175 lines, a square dot shape, and a screen angle of 45 °, and the formed halftone image is fixed to form an image. Using a device capable of reciprocating at a constant speed by applying a load while facing the unprotected protective layer surface, the area in contact with the halftone image and the protective layer surface is 1c.
mx 2cm (1cm width direction), weight 300g / c
After applying a load of m and reciprocating 5 times at a transport speed of 50 cm / sec or a transport speed of 10 cm / sec and a transport distance of 20 cm, the rubbed surface was observed and the degree of scratching was evaluated according to the following criteria.

◎: The halftone dot image surface was observed with a microscope and no damage was observed on the protective layer. ○: The halftone dot image surface was observed with a microscope and no damage was observed on the protective layer. ×, scratches reaching the colorant layer are observed. ×: Penetration scratches are observed when the dot image is observed with transmitted light.

-Evaluation of resistance to film cleaner- A halftone dot image of 50% was formed, and the formed halftone image was fixed, and a film cleaner 1 [manufactured by Makoto Chemical Co., Ltd., MC Hycline ECO] The film cleaner 2 [New Film Cleaner NF-7, manufactured by Koyo Chemical Co., Ltd.] was sufficiently dropped, and allowed to stand for 5 seconds. (Made by Co., Ltd.), the contact area is 1 cm × 2 cm (1 cm in the width direction), and the weight is 5 cm.
A load of 00 g / cm ² was applied, and the transport speed was 85 cm / sec.
It reciprocated 10 times at a transport distance of 20 cm. Before attaching the film cleaner and after hanging the film cleaner and rubbing with a soft pad, the transmission density was measured at any 30 points using a densitometer [X
-Rite: X-rite 310TR], and the density difference ΔOD of the average density was evaluated.

◎: Average density difference is less than 0.010 ○: Average density difference is 0.010 or more and less than 0.025 Δ: Average density difference is 0.025 or more and less than 0.050 ×: Average density difference is 0.050 Table 1 shows the results.

[0096]

[Table 1]

Example 2 A coating liquid for forming a filling layer having the following composition was prepared, applied and dried on the image forming layer of Example 1, and then dried at 60 ° C. for 48 hours.
Aging was performed for a time to form a sealing layer having a thickness of 0.10 μm.

<Coating Liquid for Forming Filler Layer> Phenoxy resin [Phenoxy resin PKHH manufactured by Phenoxy Associates Co., Ltd.] 4.0 parts Polyisocyanate compound [Coronate HX manufactured by Nippon Polyurethane Industry Co., Ltd.] 1.0 parts Toluene 120 parts 80 parts of cyclohexanone Next, the coating liquid 1 for forming the protective layer of Example 1 was changed to the following composition, coated and dried on the above-mentioned filling layer by a reverse bar coater, and then irradiated with UV light under a nitrogen atmosphere. Irradiation [Light source: 200W high-pressure mercury lamp, irradiation distance: 100m
m, irradiation time: described in Table 2], and cured to form a protective layer having the film thickness shown in Table 2.

Then, the release sheet of Example 1 was faced, the protective layer face and the adhesive layer face of the release sheet were faced, and heated and pressed [roll temperature: 65 ° C., transport speed: 80 mm
/ Sec, pressure 6.0 kg / cm] to produce an integrated image forming material on which a release sheet is bonded.

Using this image forming material, an image was formed in the same manner as in Example 1. Based on the same criteria as in Example 1, the obtained images were evaluated for resolution, stains on exposed portions, film cleaner resistance, and scratch resistance.

<Protective Layer Forming Coating Solution 6> Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate 6.5 parts Bisphenol A glycidyl ether 1.0 part 1,4-butanediol glycidyl ether 1.3 Part triarylsulfonium hexafluoroantimonate 0.7 part polyethylene wax dispersion (active ingredient 15% by weight) [Microflat CE-155 manufactured by Koyo Chemical Co., Ltd.] 1.67 parts silica [Fuji Silysia Chemical Ltd.] Silo Hobic 200] 0.25 parts Toluene 90 parts Methyl ethyl ketone 90 parts Cyclohexanone 20 parts <Coating liquid 7 for forming protective layer> Water-added bisphenol A diglycidyl ether 0.4 parts 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate 2.6 parts Sorbitol polyglycidyl ether 4.2 parts Epoxidized soybean oil 0.4 parts Polyethylene wax dispersion (active ingredient 15% by weight) [Micro flat CE-155, manufactured by Koyo Chemical Co., Ltd.] 2.33 parts Silica (Surface treated with alkylsilane) [Admafine Co., Ltd., Admafine SO-C2] 0.5 parts Silicone oil [Shin-Etsu Chemical Co., Ltd., X-22-343] 0.05 parts Triarylsulfonium hexa Fluoroantimonate 0.6 part Toluene 90 parts Methyl ethyl ketone 90 parts Cyclohexanone 20 parts <Protective layer forming coating liquid 8> EO-modified tetrabromo BPA dimethacrylate 3.0 parts [Daiichi Kogyo Seiyaku Co., Ltd., New Frontier BR42M] Penta Erythritol triacrylate 3.5 parts [Toa Gosei Chemical Industry Alonix M305 manufactured by Co., Ltd.] Polymethyl methacrylate resin [Dianal BR83 manufactured by Mitsubishi Rayon Co., Ltd.] 2.0 parts Polyethylene wax dispersion (active ingredient 13% by weight) [Microflat N manufactured by Koyo Chemical Co., Ltd.] -13] 3.85 parts Benzophenone 0.5 parts Michler's ketone 0.5 parts Methyl ethyl ketone 180 parts Cyclohexanone 20 parts <Protective layer forming coating liquid 9> Dipentaerythritol hexaacrylate 4.0 parts [Nippon Kayaku Co., Ltd. Kayarad DPHH] Isocyanuric acid EO-modified triacrylate 3.0 parts [Toa Gosei Chemical Industry Co., Ltd., Alonix M315] Silicone-modified resin [Dainichisei Co., Ltd., Dialomer SP2105] 1.0 part Polyethylene wax dispersion (Active ingredient 13% by weight) [Koyo Chemical Co., Ltd. 2.31 parts Silica [Silohobic 200, manufactured by Fuji Silysia Chemical Ltd.] 0.2 parts Butyl stearate 0.5 parts Benzophenone 0.5 parts Michler's ketone 0.5 parts Toluene 90 Parts 90 parts of methyl ethyl ketone 20 parts of cyclohexanone The results are shown in Table 2.

[0102]

[Table 2]

Example 3 The protective layer forming coating liquid 1 of Example 1 was changed to the following composition, and the protective layer forming coating liquid was mixed and stirred to generate heat. After stirring for 1 hour, 700 parts by weight of methanol was added. This was added to prepare a coating liquid for forming a protective layer. This protective layer forming coating liquid was applied on the image forming layer of Example 1 by a reverse bar coater application, dried, and then heat-treated at 100 ° C. for 1 minute to form a protective layer having a film thickness shown in Table 3. .

Then, the release sheet of Example 1 was faced, the protective layer face and the adhesive layer face of the release sheet were faced, and heated and pressed [roll temperature: 80 ° C., transport speed: 80 mm
/ Sec, pressure 6.0 kg / cm] to produce an integrated image forming material on which a release sheet is bonded.

Using this image forming material, an image was formed in the same manner as in Example 1. In the obtained image, Example 1
The resolution, the stain on the exposed portion, the film cleaner resistance and the scratch resistance were evaluated according to the same criteria as described above.

<Protective Layer Forming Coating Solution 10> Tetraethoxysilane 50.0 parts Fluorine / polyethylene WAX dispersion (active ingredient 40%) [Koyo Chemical Co., Ltd., Microflat CJ-204] 2.5 parts Distilled water 86.4 parts Methanol 10.8 parts Phosphoric acid (85%) 0.08 parts <Protective layer forming coating liquid 11> Tetraethoxysilane 45.0 parts Tetraethoxy titanate 5.0 parts Fluorine / polyethylene WAX dispersion (Active ingredient 40%) [Micro flat CJ-204, manufactured by Koyo Chemical Co., Ltd.] 1.5 parts Distilled water 21.6 parts Methanol 10.8 parts Nitric acid 0.05 parts <Coating liquid 12 for forming protective layer> Tetraethoxysilane 45.0 parts γ-glycidoxypropyltrimethoxysilane 5.0 parts Polyethylene wax dispersion (active ingredient 40%) [Koyo Chemical Co., Ltd. Loflat CJ-173] 1.5 parts Distilled water 86.4 parts Methanol 10.8 parts Phosphoric acid (85%) 0.08 parts Example 4 The protective layer forming coating liquid 1 of Example 1 was changed to the following composition. The coating solution for forming a protective layer was adjusted by heating, and the resin was dissolved by stirring while heating to 50 ° C., and further stirred for 1 hour to prepare a coating solution for forming a protective layer. This protective layer forming coating liquid was applied on the image forming layer of Example 1 by a reverse bar coater application, dried, and then heat-treated at 100 ° C. for 1 minute to form a protective layer having a film thickness shown in Table 3. .

<Protective Layer Forming Coating Solution 13> Monomethyltrimethoxysilane 10.0 parts Polyvinyl butyral (active ingredient 7.7%) [Eslek KX-1 manufactured by Sekisui Chemical Co., Ltd.] 129.9 parts Polyacryl Acid derivative [Sumikagel, manufactured by Sumitomo Chemical Co., Ltd.] 10.0 parts Silica [Sylysia 350, manufactured by Fuji Silysia Chemical Ltd.] 10.0 parts Polyethylene wax dispersion (active ingredient 40%) [Gifu Shellac Manufacturing Co., Ltd.] Place, A101] 3.75 parts 1.0 parts of sodium acetate 640 parts of distilled water 640 parts of isopropyl alcohol Then, the release sheet of Example 1 was faced, the protective layer face and the adhesive layer face of the release sheet were faced, and heated and pressed. Processed [roll temperature; 80 ° C, transport speed: 80 mm / sec, pressure 6.0 kg / cm], integrated image type with release sheet attached The material was produced.

Using this image forming material, an image was formed in the same manner as in Example 1. The obtained image was evaluated for resolution, stain on the exposed portion, film cleaner resistance and scratch resistance on the same basis as in Example 1.

Example 5 The following diluent was mixed with the protective layer forming coating liquid 10 of Example 3 to prepare a protective layer forming coating liquid 14. This protective layer forming coating liquid was applied on the image forming layer of Example 1 by a reverse bar coater application, dried, and then heat-treated at 100 ° C. for 1 minute to form a protective layer having a film thickness shown in Table 3. .

Then, the release sheet of Example 1 was faced, the protective layer face and the adhesive layer face of the release sheet were faced, and heated and pressed [roll temperature: 80 ° C., transport speed: 80 mm
/ Sec, pressure 6.0 kg / cm] to produce an integrated image forming material on which a release sheet is bonded.

Using this image forming material, an image was formed in the same manner as in Example 1. The obtained image was evaluated for resolution, stain on the exposed portion, film cleaner resistance and scratch resistance on the same basis as in Example 1.

<Diluent> Pyrogallol-acetone condensate 3.5 parts Polypropylene glycol monomethyl ether (average molecular weight 270) 5.0 parts Silica [Thyristia 350, manufactured by Fuji Silysia Chemical Ltd.] 0.15 part Surfactant [ Megafac F177, manufactured by Dainippon Ink and Chemicals, Inc.] 0.8 parts Methanol 800 parts Propylene glycol monomethyl ether 270 parts The results of Examples 3 to 5 are shown in Table 3.

[0113]

[Table 3]

Example 6 The following coating solution for forming an intermediate layer was prepared, and the prepared coating solution for forming an intermediate layer was coated with a transparent polyethylene terephthalate film having a thickness of 100 μm on one side by corona discharge treatment [Toray Industries, Inc.]
Co., Ltd., Lumirror T60], coated with a reverse bar coater, dried, and heat-treated at 100 ° C. for 5 minutes.
An intermediate layer having the thickness described in Table 4 was formed.

<Intermediate layer forming coating liquid 1> Polyisocyanate compound [Nippon Polyurethane Industry Co., Ltd., Coronate 3041] 1.0 part Toluene 90 parts Methyl ethyl ketone 90 parts Cyclohexanone 20 parts <Intermediate layer forming coating liquid 2> Intermediate The polyisocyanate compound of the layer forming coating solution 1 was changed to a polyisocyanate compound [Coronate 2030 manufactured by Nippon Polyurethane Industry Co., Ltd.] <Intermediate layer forming coating solution 3> Change to isocyanate compound [Millionate MR200 manufactured by Nippon Polyurethane Industry Co., Ltd.] <Intermediate layer forming coating liquid 4> Polyisocyanate compound [Corronate HX manufactured by Nippon Polyurethane Industry Co., Ltd.] 0.8 parts Polyurethane resin [Toyobo Co., Ltd. Co., Ltd., Byron UR4122] 0.2 parts torr Ene 90 parts Methyl ethyl ketone 90 parts Cyclohexanone 20 parts On the intermediate layer prepared as described above, the image forming composition prepared in Example 1 was ultrasonically dispersed, and then subjected to extrusion-type extrusion coating onto the intermediate layer. Coating and drying, and then using a heat roll, at a temperature of 100 ° C. and a linear pressure of 150 k
A calendering treatment was performed at a transfer rate of 60 m / sec at 60 g / cm, followed by aging at 60 ° C. for 120 hours to form an image forming layer having a thickness of 0.90 μm.

Next, the coating liquid 1 for forming a protective layer prepared in Example 1 was applied to the image forming layer by a reverse bar coater after ultrasonic dispersion, and then dried for 60 minutes.
Aging was performed at 72 ° C. for 72 hours to form a protective layer having a thickness of 0.25 μm.

Then, the release sheet of Example 1 was faced, the protective layer face and the adhesive layer face of the release sheet were faced, and heated and pressed [roll temperature: 80 ° C., transport speed: 80 mm
/ Sec, pressure 6.0 kg / cm] to produce an integrated image forming material on which a release sheet is bonded.

Using this image forming material, an image was formed in the same manner as in Example 1. Based on the same criteria as in Example 1, the obtained images were evaluated for resolution, stains on exposed portions, film cleaner resistance, and scratch resistance.

Table 4 shows the results.

[0120]

[Table 4]

Example 7 The coating solution 1 for forming an intermediate layer of Example 6 was changed to the following composition,
The prepared coating solution for forming an intermediate layer was applied to a 100 μm-thick transparent polyethylene terephthalate film [Lumirror T60, manufactured by Toray Industries, Inc.] on one side of which was subjected to corona discharge treatment, and dried and coated with a reverse bar coater. UV light was irradiated under the light source (light source: 200 W high-pressure mercury lamp, irradiation distance: 100 mm, irradiation time: described in Table 2) to cure, thereby forming an intermediate layer having a film thickness shown in Table 5.

<Intermediate Layer Forming Coating Solution 5> Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate 7.0 parts Bisphenol A glycidyl ether 1.0 part 1,4-butanediol glycidyl ether 1.3 Part Triarylsulfonium hexafluoroantimonate 0.7 part Toluene 90 parts Methyl ethyl ketone 90 parts Cyclohexanone 20 parts <Intermediate layer forming coating liquid 6> Water-added bisphenol A diglycidyl ether 0.5 part 3,4-epoxycyclohexylmethyl-3 , 4-epoxycyclohexanecarboxylate 4.0 parts Sorbitol polyglycidyl ether 4.7 parts Epoxidized soybean oil 0.2 parts Triarylsulfonium hexafluoroantimonate 0.6 parts Toluene 90 parts Methyl ethyl ketone 90 parts Cyclohexanone 20 parts <Intermediate layer forming coating liquid 7> EO-modified tetrabromo BPA dimethacrylate 3.0 parts [Daiichi Kogyo Seiyaku Co., Ltd., New Frontier BR42M] Pentaerythritol triacrylate 6.0 parts [Toa Gosei Chemical Industry Co., Ltd. Aronix M305] Benzophenone 0.5 part Michler's ketone 0.5 part Methyl ethyl ketone 180 parts Cyclohexanone 20 parts <Coating liquid 8 for forming intermediate layer> Dipentaerythritol hexaacrylate 5.0 parts [Nippon Kayaku Co., Ltd. Kayarad DPHH] Isocyanuric acid EO-modified triacrylate 4.0 parts [Toa Gosei Chemical Industry Co., Ltd., Aronix M315] Benzophenone 0.5 parts Michler's ketone 0.5 parts Toluene 90 parts Methyl ethyl ketone 90 parts Cyclohexanone 20 Part The same image forming layer and protective layer as in Example 6 were formed on the intermediate layer prepared as described above, and then the release sheet of Example 1 was faced. The sheets were confronted and subjected to a heat and pressure treatment [roll temperature: 80 ° C., conveyance speed: 80 mm / sec, pressure 6.0 kg / cm] to produce an integrated image forming material having a release sheet bonded thereto.

Using this image forming material, an image was formed in the same manner as in Example 1. Based on the same criteria as in Example 1, the obtained images were evaluated for resolution, stains on exposed portions, film cleaner resistance, and scratch resistance.

Table 5 shows the results.

[0125]

[Table 5]

Example 8 The intermediate layer forming coating liquid 1 of Example 6 was changed to the following composition,
The intermediate layer forming coating liquid was mixed and stirred to generate heat, and after further stirring for 1 hour, 700 parts by weight of methanol was added to prepare an intermediate layer forming coating liquid. This intermediate layer forming coating solution is
On a transparent polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) having a 100 μm-thick one-sided surface subjected to corona discharge treatment, it was coated and dried by a reverse bar coater, and then heat-treated at 100 ° C. for 1 minute. An intermediate layer having the thickness described above was formed.

<Intermediate layer forming coating liquid 9> Tetraethoxysilane 50.0 parts Distilled water 86.4 parts Methanol 10.8 parts Phosphoric acid (85%) 0.08 part <Intermediate layer forming coating liquid 10> Tetra Ethoxysilane 45.0 parts Tetraethoxy titanate 5.0 parts Distilled water 21.6 parts Methanol 10.8 parts Nitric acid 0.05 parts <Intermediate layer forming coating liquid 11> Tetraethoxysilane 45.0 parts γ-glycidoxy Propyltrimethoxysilane 5.0 parts Distilled water 86.4 parts Methanol 10.8 parts Phosphoric acid (85%) 0.08 parts On the intermediate layer produced as described above, the same image forming layer as in Example 6, After forming a protective layer, the release sheet of Example 1 was faced, the protective layer face and the adhesive layer face of the release sheet were faced, and heated and pressurized [roll temperature: 80 ° C., transport speed: 80 mm / sec. The pressure was 6.0 kg / cm] to produce an integrated image forming material having a release sheet bonded thereto.

Using this image forming material, an image was formed in the same manner as in Example 1. Based on the same criteria as in Example 1, the obtained images were evaluated for resolution, stains on exposed portions, film cleaner resistance, and scratch resistance.

Example 9 An intermediate layer forming coating liquid was prepared by changing the intermediate layer forming coating liquid of Example 6 to the following composition, and stirred while heating to 50 ° C. to dissolve the resin. The mixture was stirred for an hour to prepare a coating liquid for forming an intermediate layer. This intermediate layer forming coating liquid was applied to a thickness of 100 μm.
m on a transparent polyethylene terephthalate film [Lumirror T60, manufactured by Toray Industries, Inc.] that has been subjected to corona discharge treatment on one side, and then coated with a reverse bar coater and dried.
Heat treatment was performed at 100 ° C. for 1 minute to form an intermediate layer having the thickness shown in Table 6.

<Intermediate layer forming coating liquid 12> Monomethyltrimethoxysilane 23.0 parts Polyvinyl butyral (active ingredient 7.7%) [Eslek KX-1 manufactured by Sekisui Chemical Co., Ltd.] 129.9 parts Polyacryl Acid derivative [Sumitomo Chemical Co., Ltd., Sumikagel] 5.0 parts Silica [Fuji Silysia Chemical Ltd., Sylysia 350] 2.0 parts Sodium acetate 1.0 part Distilled water 640 parts Isopropyl alcohol 640 parts As described above The same image forming layer and protective layer as in Example 6 were formed on the intermediate layer prepared as described above, and then the release sheet of Example 1 was faced, and the protective layer face and the adhesive layer face of the release sheet were faced. A pressure treatment [roll temperature; 80 ° C., transfer speed: 80 mm / sec, pressure 6.0 kg / cm] was performed to produce an integrated image forming material on which a release sheet was bonded.

Using this image forming material, an image was formed in the same manner as in Example 1. Based on the same criteria as in Example 1, the obtained images were evaluated for resolution, stains on exposed portions, film cleaner resistance, and scratch resistance.

Table 6 shows the results of Examples 8 and 9.

[0133]

[Table 6]

Example 10 A transparent polyethylene terephthalate film having a thickness of 24 μm and easily treated on one side [manufactured by Diafoil Hoechst Co., Ltd.
T100E], an adhesive layer composition having the following composition was applied with a bar coater and dried to form an adhesive layer having a thickness of 20 μm, thereby preparing a release sheet.

<Adhesive Layer Composition> Styrene-Isoprene-based resin [Clayton D1117 manufactured by Shell Japan Co., Ltd.] 25.0 parts Silicone-modified resin [Cymac US270 manufactured by Toagosei Co., Ltd.] 5.0 parts Toluene 35. 0 parts Methyl ethyl ketone 35.0 parts Then, the protective layer surface of the image forming material formed up to the protective layers of Examples 1 to 9 and the adhesive layer surface of the above-mentioned release sheet were opposed to each other, and heated and pressurized [roll temperature; Conveyance speed; 5
00 mm / sec, pressure 6.0 kg / cm] to produce an integrated image forming material having a release sheet bonded thereto.

The image forming material thus prepared is focused on the interface between the transparent support of the image forming material and the image forming layer, and the resolution is 2540 DPI and the screen line is determined using the postscript data (PS data). Number 120
1 / cm, halftone dot square, screen angle 0 ° dry setter [Heidelberg Prepress Co., Ltd.
After exposing the halftone dot image with a light value of 255], the film was peeled off, and the resolution, the residual ratio of the exposed portion, the scratch resistance and the film cleaner resistance were evaluated according to the following criteria.

-Evaluation of Resolution- An image is formed by using a vertical stripe pattern in the main scanning direction of the drum of 2540 DPI as PS data, and the formed vertical stripe pattern is arbitrarily extracted at 30 points in the main scanning direction, and is sub-scanned with a loupe. Observation was made in the direction, and the average number of lines / spaces per inch (this is regarded as one) and the difference between the maximum number and the minimum number (Δ number) were evaluated.

-Evaluation of dirt on exposed portion- Resolution 2540 DPI, screen ruling 120 l / c
m, halftone dot square, 0% at screen angle 45 °
Is formed, and the transmission density of the formed halftone image is measured at an arbitrary 30 points by a densitometer [X-rite: Xr
item 310TR], and the average density ODav was evaluated.

◎: Average density is less than 0.050 ○: Average density difference is 0.050 or more and less than 0.060 Δ: Average density difference is 0.060 or more and less than 0.075 ×: Average density difference is 0.075 or more .

-Evaluation of scratch resistance- 2540 DPI resolution, 120 l / c screen ruling
m, halftone dot square, 50 at screen angle 45 °
% Of the halftone dot image is formed, the halftone dot image on which the image is formed is fixed, and the surface of the protective layer on which no image is formed is faced.
Using a device capable of reciprocating at a constant speed by applying a load, apply a load of 100 g / cm with an area of 1 cm x 2 cm (1 cm in the width direction) in contact with the halftone image and the protective layer surface, and After reciprocating 5 times at 50 cm / sec or a transport speed of 10 cm / sec and a transport distance of 20 cm, the rubbed surface was observed and the degree of scratching was evaluated according to the following criteria.

◎: The halftone dot image surface was observed with a microscope and no scratch was observed on the protective layer. ○: The halftone dot image surface was observed with a microscope and no scratch was observed on the protective layer. Δ: The halftone dot image surface was observed with a microscope. ×, scratches reaching the colorant layer are observed. ×: Penetration scratches are observed when the dot image is observed with transmitted light.

-Evaluation of Film Cleaner Resistance- A halftone dot image of 50% was formed, and the formed dot image was fixed, and a film cleaner 1 [manufactured by Makoto Chemical Co., Ltd., MC Hycline ECO] or an The film cleaner 2 [New Film Cleaner NF-7, manufactured by Koyo Chemical Co., Ltd.] was sufficiently dropped and allowed to stand for 10 seconds, and then used for evaluation of abrasion resistance. (Made by Co., Ltd.)
The contact area is 1cm x 2cm (width direction is 1cm)
A load of 100 g / cm ² is applied at a transport speed of 85 cm.
10 reciprocations at a transport distance of 20 cm / sec. The transmission density after attaching the film cleaner and after hanging the film cleaner and rubbing with a soft pad was measured at any 30 points using a visual density of a densitometer [X-rite 310TR], and averaged. Density difference ΔO
D was evaluated.

A: Average density difference is less than 0.010 O: Average density difference is 0.010 or more and less than 0.025 Δ: Average density difference is 0.025 or more and less than 0.050 X: Average density difference is 0.050 Table 7 shows the results.

[0144]

[Table 7]

[0145]

According to the present invention, it is possible to obtain an ablation type image forming material which is excellent in scratch resistance and cleaner resistance of a formed image and excellent in resolution.

Continued on front page F-term (reference) 2H111 AA01 AA04 AA08 AA26 AA35 AB01 BA02 BA03 BA04 BA09 BA32 BA33 BA35 BA53 BA54 BA55 BA62 BA74 BA76 BB05 DA02 DA04 HA05 HA14 HA23 HA35

Claims (15)

[Claims] 1. An ablation type image forming material comprising a transparent support and an image forming layer and a protective layer containing at least a resin having a urethane bond in the molecule and a wax in this order. 2. A resin having an active hydrogen group in the molecule and a coating solution containing an isocyanate compound are coated on the image forming layer, dried and cured to form the resin having the urethane bond in the molecule. The ablation-type image forming material according to claim 1, wherein 3. The ratio of the isocyanate group equivalent of the isocyanate compound in the coating liquid to the hydroxyl equivalent of the resin having an active hydrogen group in the molecule is 1 or more. Ablation type image forming material. 4. An image forming layer and a protective layer are provided in this order on a transparent support, and the protective layer is coated with a coating liquid containing a compound curable by an active energy ray on the image forming layer, An ablation-type image forming material, which is a resin layer cured by irradiation with an active energy ray. 5. The ablation method according to claim 4, wherein the compound curable by the active energy ray is a compound having an unsaturated double bond in a molecule or a compound having an epoxy group in a molecule. Mold image forming material. 6. An ablation type image forming material comprising an image forming layer and a protective layer formed of a metal oxide on a transparent support in this order. 7. The protective layer according to claim 1, wherein the protective layer contains at least one selected from inorganic fine particles, organic fine particles, a silicone compound and a fluorine compound. Or the ablation type image forming material according to 6. 8. The method according to claim 1, wherein the protective layer contains a compound represented by the following general formula (1).
8. The ablation-type image forming material according to 3, 4, 5, 6, or 7. General formula (1) RS [where S is COOH, COOM, SO ₃ H, SO ₃ M,
CONH ₂ , SO ₃ NH ₂ or N ⁺ R ₁ R ₂ R ₃ X,
Represents an alkali metal, X represents a counter anion, R represents a saturated or unsaturated hydrocarbon having 11 or more carbon atoms, and R _{1 to} R ₃ represent a saturated or unsaturated hydrocarbon having 1 or more carbon atoms.] 9. An image forming layer and a protective layer are provided on a transparent support in this order, an intermediate layer is laminated between the transparent support and the image forming layer, and the intermediate layer contains an isocyanate compound. An ablation-type image forming material, characterized by being a resin layer formed by applying a working liquid onto a transparent support, drying and curing. 10. An image forming layer and a protective layer are provided in this order on a transparent support, and an intermediate layer is laminated between the transparent support and the image forming layer, and the intermediate layer is curable by an active energy ray. An ablation-type image forming material, which is a resin layer obtained by curing a compound. 11. An image forming layer and a protective layer are provided on a transparent support in this order, an intermediate layer is laminated between the transparent support and the image forming layer, and the intermediate layer is formed of a metal oxide. An ablation-type image forming material, which is a layer. 12. The image forming layer according to claim 1, wherein the color material fine particles are a binder resin, and the color material fine particles are ferromagnetic powder. ,
The ablation-type image forming material according to 8, 9, 10 or 11. 13. The method according to claim 1, wherein a release sheet is laminated on the protective layer.
13. The ablation-type image forming material according to 7, 8, 9, 10, 11 or 12. 14. After exposing the image forming material according to claim 13 to an image by laser light from the transparent support side, peeling off the release sheet to transfer the exposed portion of the image forming layer to the release sheet. And an image forming method. 15. The image forming method according to claim 14, wherein image exposure is performed by scanning with a laser beam.