JP2000118132A - Image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the yield by improving the coating failure, improve the generation of fouling on the image surface at the time of forming an image, realize the higher resolution of an image pattern and also improve the scratching properties at the time of handling for an image forming material for forming the image by the exposure of high density energy for forming the image of high density and high resolution. SOLUTION: An image forming material is provided at least with a coloring material layer on a substrate, and polyurethane resin B1, polyester resin B2 and phenoxy resin B3 are contained as binders in the coloring material layer, and the glass transition temperature Tg of B1 and B2 is respectively 70 deg.C or higher. Also one material or more having at least a coloring material layer and an overcoat layer on the substrate and selected out of carbon black, an inorganic filler, polytetrafluoroethylene and molybdenum disulfide is contained at the ratio of 0.5-10 wt.% in the total solid content in the overcoat layer and at the ratio of 0.5-10.0 wt.%, to the inorganic pigment in the coloring material layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a high-density, high-resolution image, no pinholes in the manufacturing process, no deterioration in image quality in the image forming process, and less scratches after image formation. It relates to an image forming material.

[0002]

2. Description of the Related Art Heretofore, there has been known a recording method in which light energy such as a laser beam is focused and irradiated on a recording material to melt or deform a part of the material, or to scatter, burn or evaporate. These are dry treatments that do not require treatment liquids such as chemicals, and have the advantage that a high contrast can be obtained by melting and deforming, scattering and / or evaporating and removing only the light irradiation part (ablation). It is used as a resist material, an optical recording material such as an optical disk, and an image forming material that makes itself a visible image.

[0003] For example, Japanese Patent Application Laid-Open Nos.
JP-A-105638 and JP-A-62-115153 disclose a method of forming a resist pattern by photodecomposing a binder resin by pattern exposure and materials for the same, which are disclosed in JP-A-55-132536, JP-A-57-27788, and JP-A-57-27788. 57
JP-A-103137 discloses that an inorganic compound thin film provided by a vapor deposition method is exposed to light to record information by melting deformation of the film.
No. 87, No. 6-40163 and the like, a material for information recording by removing a colored binder layer by photothermal conversion,
U.S. Pat. No. 4,245,003 and the like each disclose an image forming material having an image forming layer containing graphite or carbon black.

[0004]

When the image forming method disclosed in the above-mentioned U.S. Patent is used, a high-density and high-resolution image can be obtained, but pinholes, which are failures during the manufacturing process, and colors that occur during image formation are generated. There was no effective means for surface dirt, high resolution, and scratches during handling due to materials and binders. In the past, coating properties and transportability have been improved by changing the coating method, contamination measures with undercoating layers, high resolution measures with additives, transfer of foil to the image forming layer surface,
Although countermeasures against scratches in lamination processing and the like have been taken, it has been difficult to employ them because the processing steps are lengthened and costs are increased.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an image forming material which forms an image by exposure to high-density energy light capable of obtaining a high-density, high-resolution image. Improvement in yield by improving
An object of the present invention is to provide an image forming material which is more reliable and cheaper than conventional ones by improving the stain on the image surface during image formation, increasing the resolution of the image pattern, and improving the abrasion during handling.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide at least a color material layer on a support, wherein the color material layer has a polyurethane resin (B1) and a polyester resin (B2) as a binder. ) And phenoxy resin (B
3), wherein the glass transition temperature (Tg) of each of B1 and B2 is 70 ° C. or more, and the binder is contained in a relation of B1> B2 and B1> B3 by weight. The amount is 10 to 30% by weight based on all the colorants and inorganic compounds contained in the colorant layer, and at least the colorant layer and the overcoat layer are provided on the support, and carbon black, inorganic 1 selected from filler, polytetrafluoroethylene and molybdenum disulfide
0.5 to 10% by weight of the total solid content in the overcoat layer and 0.5 to
-10.0% by weight.

Hereinafter, the present invention will be described in detail.

The image forming material of the present invention has a colorant layer and an overcoat layer if necessary on a transparent support, and contains a polyurethane-based resin, a polyester-based resin and a phenoxy resin as a binder main component. It is characterized by containing at least one material selected from carbon black, an inorganic filler, polytetrafluoroethylene and molybdenum disulfide.

As the support, acrylates, methacrylates, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, nylon, aromatic polyamide, polyether Examples of the transparent support include resin films of ether ketone, polysulfone, polyether sulfone, polyimide, and polyetherimide, and further, a resin film obtained by laminating two or more layers of the resin. In the present invention, the transparent support is a support capable of transmitting light of the wavelength of the exposure light source, and is preferably stretched and heat-set into a film in terms of dimensional stability, and does not impair the effects of the present invention. In addition, fillers such as titanium oxide, zinc oxide, barium sulfate, and calcium carbonate may be added, and when used for medical purposes, a dye may be added for coloring blue. The thickness of the support is about 10 to 500 μm, preferably 25 to 250 μm.

In the present invention, the support is used in order to improve adhesiveness and coatability within a range not to impair the effects of the present invention.
Modification using known surface modification technology such as corona discharge treatment and anchor coating treatment, antistatic on the back of the support,
It may have a layer such as a back coat layer for the purpose of scratch prevention, transportability, and prevention of feeding of a plurality of sheets. In addition, when providing an anchor coat or a back coat layer, 0.001 to 10 μm
It is preferable that the thickness is about 0.005 to 5 μm.

In the present invention, the term "image forming layer" is a general term for layers including all of an overcoat layer, a coloring material layer, an anchor coat layer and the like on the front side of the image forming material.

As the image forming layer, a light-to-heat conversion layer and a color material layer may be laminated, or a plurality of each may be provided. Further, the color material layer may also serve as the light-heat conversion layer. The colorant contained in the image forming layer can be used without any particular limitation as long as the bonding force between the support of the exposed portion and the image forming layer can be reduced in the image forming method of the present invention described later. In order to efficiently reduce the bonding strength between the support of the exposed portion and the image forming layer and to provide image legibility, 300-80
It is preferable to use a substance having absorption in the wavelength range of 0 nm as the coloring agent. The photothermal conversion substance and the substance having absorption in the wavelength range of 300 to 800 nm may be used alone or in combination of two or more. You may mix and use. Also, 300
In the case of a substance having an absorption in a wavelength range of from about 800 nm to a substance which can also act as a photothermal conversion substance, only a substance which also serves as a photothermal conversion substance may be used as a coloring agent. Such a light-to-heat conversion substance can use an organic compound and / or an inorganic compound.
For example, dyes and dyes having an absorption in the wavelength range of 600 to 1200 nm can be mentioned. Specifically, cyanine dyes, rhodocyanine dyes, oxonol dyes, carbocyanine dyes, dicarbocyanine dyes, and tricarbocyanine dyes , Tetracarbocyanine dyes, pentacarbocyanine dyes, styryl dyes, pyrylium dyes, phthalocyanine dyes, gold-containing dyes, and the like.
m. Rev .. 92, 1197 (1992) and the like. Examples of the inorganic compound include graphite, carbon black, cobalt tetroxide, iron oxide, chromium oxide, copper oxide, and titanium black.

The substance having absorption in the wavelength range of 300 to 800 nm is an organic compound and / or a light-to-heat conversion substance.
Or, an inorganic compound can be used. Examples of the organic compound include conventionally known various dyes, dyes, and organic pigments, and examples of the inorganic compound include a conventionally known inorganic pigment and metal oxide powder. , Metal nitride powder, metal carbide powder, metal sulfide powder, and the like, and various magnetic powders used for magnetic paints and the like can also be suitably used in the present invention.

In the case where only the above-mentioned coloring agent which absorbs light in the wavelength range of 300 to 800 nm, which also functions as a light-to-heat converting material, is used, the coloring agent is present in the layer in a dispersed state, and It is preferable that the agent itself is not porous since an image having a lower residual ratio of the image forming layer in the exposed portion on the support can be obtained in the image forming method described below. Examples of such a coloring agent include inorganic compounds having absorption in a wavelength range of 300 to 800 nm, such as the above-described metal oxide powder, metal nitride powder, metal carbide powder, and various magnetic powders used in magnetic inks and the like. Among them, when a high-resolution image is obtained, those having a particle diameter of 0.5 μm or less, more preferably 0.3 μm or less are more preferable. For example, when using a magnetic powder among them, a ferromagnetic iron oxide powder, a ferromagnetic metal powder, a cubic plate-like powder and the like can be appropriately selected and used, and among them, a ferromagnetic metal powder is preferably used. be able to. The shape of the ferromagnetic powder preferably has a major axis diameter of 0.30 μm or less, and preferably 0.20 μm or less. By using such a ferromagnetic powder, an image having a small ablation portion residual rate can be obtained. In addition, the surface property of the image forming layer is improved. The content of the colorant contained in the color material layer is about 10 to 99% by weight, preferably 3% by weight, of the components forming the color material layer.
0 to 95% by weight.

The coloring material layer binder contains a polyurethane resin (B1), a polyester resin (B2) and a phenoxy resin (B3) as main components.
In the present invention, it is essential that the glass transition point, so-called Tg, of each of B1 and B2 is 70 ° C. or more.
And the binder is B1> B2 and B1> B3 by weight.
It is preferable that the content is 10 to 30% by weight based on all the colorants and inorganic compounds contained in the color material layer. Further, within a range not deteriorating the performance, vinyl chloride-based resin such as vinyl chloride-vinyl acetate copolymer, polyolefin-based resin such as butadiene-acrylonitrile copolymer, polyvinyl acetal-based resin such as polyvinyl butyral, and cellulose such as nitrocellulose. Resin, styrene resin such as styrene-butadiene copolymer, acrylic resin such as polymethyl methacrylate,
Polyamide, phenol resin, epoxy resin, and the like can be added.

The coating solution for forming an image forming layer containing the above-described colorant is applied on a transparent support, and then cured. As the curing agent, an isocyanate-based curing agent mainly containing isocyanate is used. Curing can be performed by a conventionally known curing method such as thermal curing, active energy curing, and moisture curing. To sufficiently perform curing, the image forming layer is cured by thermal curing and / or active energy ray curing. It is preferred that As aromatic isocyanates, tolylene diisocyanate (TDI), 4,4'-
Diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), naphthylene diisocyanate (NDI) and the like can be used. As the thermosetting binder resin used for the thermosetting described above, and a curing agent added as necessary, a binder resin having a hydroxyl group, a carboxyl group or a sulfonic acid group and a curing agent having an isocyanate group, containing an epoxy group are included. A binder resin or a curing agent, an amino group-containing binder resin or a curing agent or a binder resin containing an acid anhydride or a curing agent, and the like.A resin that can be thermoset using a catalyst or the like may be appropriately selected. Can be used.

The content of the binder resin contained in the image forming layer is about 1 to 90% by weight of the components for forming the image forming layer.
Preferably it is 5-70% by weight. The curing agent or catalyst is used in an amount of usually 0.1 to 200 parts by weight, more preferably 0.5 to 1 part by weight, per 100 parts by weight of the thermosetting binder resin.
Add and mix in a range of 00 parts by weight.

In the active energy ray curing, a combination of a conventionally known compound having an ethylenically unsaturated double bond or a compound having an epoxy group with a polymerization initiator can be used. The image forming layer may contain additives such as a lubricant, a durability improver, a dispersant, and an antistatic agent, in addition to the above components, 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, and carbon fluoride, and examples of the durability improver include polyisocyanate. Can be. Examples of the dispersant include fatty acids having 12 to 18 carbon atoms, such as lauric acid and stearic acid, and amides, alkali metal salts, and alkaline earth metal salts thereof; polyalkylene oxide alkyl phosphates, lecithin, trialkyl polyolefinoxy Quaternary ammonium salts;
Examples include an azo compound having a carboxyl group and a sulfone group. In the above-described thermosetting binder resin, active energy ray-curable compound or binder resin, -SO ₃ M, -OSO ₃ M , -COOM and -PO (OM ₁ ) ₂ wherein M represents a hydrogen atom or an alkali metal, and M ₁ represents a hydrogen atom, an alkali metal or an alkyl group. Can also be used as a dispersant for improving dispersibility.

Examples of the antistatic agent include cationic surfactants, anionic surfactants, nonionic surfactants, polymer antistatic agents, conductive fine particles, and the like. , P. And the compounds described in 875-876 and the like.

In the present invention, it is essential that at least one material selected from carbon black, an inorganic filler, polytetrafluoroethylene and molybdenum disulfide is contained in the overcoat layer and the colorant layer. Carbon black has a specific surface area, so-called BET, of 100 m ² / g.
The following are preferred. As the inorganic filler, TiO
₂ , BaSO ₄ , ZnS, MgCO ₃ , CaCO ₃ , Zn
O, CaO, WS ₂ , MgO, SnO ₂ , Al ₂ O ₃ , α-
Fe ₂ O ₃ , α-FeOOH, SiC, CeO ₂ , BN,
SiN, MoC, BC, WC, titanium carbide, corundum, artificial diamond, garnet, garnet, quartzite, triboli, diatomaceous earth, dolomite and the like can be mentioned. Polytetrafluoroethylene and molybdenum disulfide preferably have an average particle size of 0.2 to 1.0 μm.

The amount of the above-mentioned additives is preferably 0.5 to 10% by weight based on all the light-to-heat conversion materials, coloring agents and inorganic compounds contained in the colorant layer.

According to the present invention, an overcoat layer is laminated within a range not to impair the effect, and at least one material selected from carbon black, an inorganic filler, polytetrafluoroethylene and molybdenum disulfide is contained in the overcoat layer. It is characterized by.

The overcoat layer may contain waxes in addition to the binder resin as a main component. As the wax, beeswax, candelilla wax, paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax and the like can be used.
The particle size is preferably 1 μm to 20 μm. As a main component of the overcoat layer, using a resin having self-supporting properties, it may be directly laminated on the image forming layer by a method such as coating or hot melt extrusion, or as a support as described above. An overcoat layer may be formed by applying an overcoat layer on a resin film to be used by a method such as coating or hot-melt extrusion as a peeled body, facing the image forming layer and bonding. As the binder resin which is a main component of the overcoat layer, a resin used in the image forming layer can be used.

In the present invention, at least one selected from carbon black, an inorganic filler, polytetrafluoroethylene and molybdenum disulfide is added to the coating solution for the colorant layer and the overcoat layer.

First, a colorant, a binder resin, and a solvent are mixed, kneading and dispersion treatment is performed, and then the concentration is adjusted to an appropriate concentration for coating. Carbon black, inorganic filler,
Polytetrafluoroethylene and molybdenum disulfide are
It may be added at any step from the kneading stage to the pre-coating stage.
The form is preferably a dispersion or a paste.

The term "dispersion" as used herein refers to a liquid in which a material is uniformly distributed in a solvent. The term “paste” as used herein refers to a powder obtained by subjecting a powder to a dispersion treatment with a binder and suspending the powder in a solvent. As described above, the effects of the present invention are significantly improved by adding a dispersion or a paste.

The adhesive layer used for the peeling body to be bonded to the image forming layer may be any of those having adhesiveness or tackiness at room temperature, and those exhibiting adhesiveness or tackiness by applying heat or pressure. For example, it can be formed by appropriately selecting a resin having a low softening point, an adhesion-imparting agent, and a thermal solvent.

Examples of the resin having a low softening point include ethylene copolymers such as ethylene-vinyl acetate and ethylene-ethyl acrylate; polystyrene resins such as styrene-butadiene, styrene-isoprene and styrene-ethylene-butylene; polyester resins; Polyolefin resins such as polyethylene and polypropylene; polyvinyl ether resins; acrylic resins such as polybutyl methacrylate;
Ionomer resins; cellulosic resins; epoxy resins; vinyl chloride resins such as vinyl chloride-vinyl acetate copolymers, and the like. Examples of the adhesion-imparting agent include rosin, hydrogenated rosin, rosin maleic acid, polymerized rosin and Unmodified or modified products such as rosin phenol, terpenes, petroleum resins and modified products thereof, and the like. Examples of the heat solvent include compounds which are solid at ordinary temperature and which reversibly liquefy or soften when heated, and specifically, terpineol, menthol, acetamide, benzamide, coumarin, benzyl cinnamate, diphenyl ether, crown ether, Monomolecular compounds such as camphor, p-methylacetophenone, vanillin, dimethoxybenzaldehyde, p-benzylbifevir, stilbene, margaric acid, eicosanol, cetyl palmitate, stearamide, behenylamine, beeswax, candelilla wax, paraffin wax , Ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax and other waxes, ester gum, rosin maleic resin, rosin pheno Rosin derivatives such as Le resin, phenol resin,
Ketone resin, epoxy resin, diallyl phthalate resin,
Examples include terpene hydrocarbon resins, cyclopentadiene resins, polyolefin resins, polycaprolactone resins, and high molecular compounds represented by polyolefin oxides such as polyethylene glycol and polypropylene glycol.

The thickness of the adhesive layer is about 0.1 to 40 μm, preferably 0.3 to 30 μm, and the thickness of the whole peeled body including the support or the thickness of the peeled layer is 0.1 to 200 μm.
Degree, preferably 0.5 to 100 μm.

Solvents used in a coating method for preparing a coating solution by dispersing or dissolving the components in a solvent and applying and drying this coating solution include water, alcohols (eg, ethanol and propanol), cellosolves and the like. (Eg, methyl cellosolve, ethyl cellosolve), aromatics (eg, toluene, xylene, chlorobenzene), ketones (eg, acetone, methyl ethyl ketone), ester solvents (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, Dioxane), chlorinated solvents (eg, chloroform, trichloroethylene), amide solvents (eg, dimethylformamide, N-methylpyrrolidone), dimethylsulfoxide, and the like. Alternatively, a layer can be formed by melting a forming component with a hot melt and extruding.

Bonding and adhesion of the peeled body to the image forming layer can be performed by pressing or heating and pressing. The pressurizing or heat-pressing treatment can be used without any particular limitation as long as it can increase the adhesion and can pressurize or heat-press without mixing bubbles or the like. In the case where the heating and pressurizing treatment is performed on a stamper or a stamper, a thermal head, a heat roll, a hot stamp, or the like can be used. The pressure when using a pressure roll is usually 0.1 to 20 kg / cm, preferably 0.5 to 20 kg / cm.
10 kg / cm, and the conveying speed is usually 0.1 to
The pressure is 200 mm / sec, preferably 0.5 to 100 mm / sec. The pressure when using a stamper is usually 0.05 to 10 kg / cm ² , preferably 0.5 to 5 k.
g / cm ² , and the pressurization time is usually 0.1 to 50 seconds, preferably 0.5 to 20 seconds. Further, the thermal head can be used as it is under the conditions used for ordinary melt transfer, sublimation transfer, and the like. When using a heat roll, the heating temperature is usually 60 to 200 ° C., preferably 8 to 200 ° C.
The temperature is in the range of 0 to 180 ° C. and the pressure is usually 0.1 to 20.
kg / cm, preferably 0.5 to 10 kg / cm, and the conveying speed is usually 0.1 to 200 mm / sec, preferably 0.5 to 100 mm / sec. Heating temperature is usually 60 to 200
° C, preferably in the range of 80 to 150 ° C, and as the pressure,
Usually 0.05 to 10 kg / cm ² , preferably 0.5 to
5 kg / cm ² , and the heating time is usually 0.1 to 50
Seconds, preferably 0.5 to 20 seconds. The form of the image forming material is supplied in a form in which an image forming sheet on which an image forming layer is laminated and a release sheet on which an adhesive layer is laminated for pulling out the image forming layer are laminated. The image forming material may be in the form of a sheet or a roll. The packaging form of the image forming material is a tray or a cartridge when it is in the form of a sheet, and when it is pulled out from the tray or the cartridge, it is sequentially pulled out from the outermost and transported. In the case of a roll, the cartridge is taken out as it is or a cartridge, and is sequentially pulled out from the outermost portion and transported.

The image forming material is exposed imagewise to high-density energy light to reduce the bonding force between the support at the exposed portion and the image forming layer. Is transferred to the adhesive layer of the release sheet, and an unexposed portion of the image forming layer is left on the image forming sheet support to form an image. In this method, the exposure direction of the light energy is preferably from the image forming sheet support side, and furthermore, the image forming layer in the image exposed portion does not break down, and only the adhesive force between the support and the image forming layer decreases. Alternatively, it is preferable to perform the image exposure so that the image exposed portion can be uniformly pulled out to the release sheet side. The exposure of the light energy does not cause the destruction of the image-forming layer in the image-exposed portion, and only reduces or eliminates the bonding force between the support and the image-forming layer. In addition to breakage and scattering, a phenomenon in which a crack occurs in an image forming layer in an image exposed portion may be used. The image exposure can be used without particular limitation as long as the light source causes a decrease in the bonding force between the support of the exposed portion and the image forming layer. inside that,
In order to obtain high resolution, electromagnetic waves whose energy application area can be narrowed down, in particular, ultraviolet light, visible light, and infrared light having a wavelength of 1 nm to 1 mm are preferable. As a light source to which such light energy can be applied, for example, 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 by adjusting the exposure distance, time, and intensity according to the type of the exposure sheet. In the case of performing the batch exposure of the above energy, a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be overlapped and exposed. When an array type light source such as a light emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp, or a tungsten lamp is exposed and controlled by an optical shutter material such as a liquid crystal or PLZT, a digital signal corresponding to an image signal is used. Exposure can be performed. In this case, direct writing can be performed without using a mask material.
However, in this method, a new optical shutter material is required in addition to the light source. Therefore, in the case of digital exposure, it is preferable to use a laser as the light source.

When laser light is used as a light source,
It is possible to form a latent image by scanning light according to image data by narrowing the light into a beam, and using a laser as a light source, it is easy to narrow the exposure area to a very small size and high resolution images Formation is possible. As the laser light source used in the present invention, generally well-known solid lasers such as ruby laser, YAG laser, and glass laser; He-Ne laser, Ar ion laser, Kr ion laser, CO ₂ laser, CO ₂ laser,
Laser, He-Cd laser, N ₂ laser, gas laser such as excimer laser; InGaP laser, AlGaAs laser, GaAsP laser, In
GaAs laser, InAsP laser, CdSnP ₂
Semiconductor lasers such as lasers and GaSb lasers; chemical lasers, dye lasers, and the like. Among these, visible light having a wavelength of 600 to 1200 nm to near-infrared light can be used to efficiently reduce the bonding force. The use of a laser in the region is preferable in terms of sensitivity because light energy can be efficiently converted to heat energy. After the exposure, the image forming material may be subjected to pressure or heat / pressure treatment as needed. The above-described method can be used for the pressurizing or heating / pressing treatment.

[0035]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 100 parts by weight of Fe—Al ferromagnetic metal powder (major axis diameter: 0.14 μm, BET: 53 m ² / g) 10 parts by weight of polyurethane resin (UR-8200 Tg, manufactured by Toyobo Co., Ltd.) : 73 ° C) Polyester resin 3 parts by weight (Toyobo Co., Ltd., Byron V280 Tg: 72 ° C) Phenoxy resin 2 parts by weight (Phenoxy Associates Co., Ltd. PKHH Tg: 100 ° C) Phosphate ester dispersant (Toho) 3 parts by weight of isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) 3 parts by weight of polytetrafluoroethylene 5 parts by weight of cyclohexanone 100 parts by weight of methyl ethyl ketone 100 parts by weight of toluene 100 parts by weight of toluene The coloring material layer composition consisting of parts by weight is 100 μm thick support (Toray Industries, Inc.)
Co., Ltd., T-60), dried, and subjected to a surface treatment with a calender to form an image forming layer having a thickness of 1.0 μm.

1 part by weight of phenoxy resin (manufactured by Phenoxy Associates: PKHH) 25 parts by weight of cyclohexanone 72 parts by weight of toluene 2 parts by weight of carbon black (Sevacarb MT, manufactured by Colombian Carbon Japan Co., Ltd.) Was prepared and applied onto the image forming layer by wire bar coating to obtain an image forming material-1 as an overcoat layer having a thickness of 0.25 μm.

Image forming material-2 was obtained in the same manner except that the binder composition of image forming material-1 was changed as follows.

Polyurethane resin 6 parts by weight (Toyobo Co., Ltd., UR-8200 Tg: 73 ° C.) Polyester resin 5 parts by weight (Toyobo Co., Ltd., Byron V280 Tg: 72 ° C.) Phenoxy resin 4 parts by weight ( Image forming material-1 except that polytetrafluoroethylene of the colorant layer composition was replaced with 5 parts by weight of α-alumina (average particle size = 0.15 μm), PKHH Tg: 100 ° C., manufactured by Phenoxy Associates Co., Ltd. Similarly, an image forming material
3 was obtained.

The image forming material was the same as the image forming material-1 except that the polytetrafluoroethylene of the colorant layer composition was replaced by 5 parts by weight of carbon black (Sevacarb MT, manufactured by Colombian Carbon Japan KK). -4 was obtained.

The polytetrafluoroethylene of the coloring material layer composition was converted to molybdenum disulfide (average particle size = 0.30 μm).
An image forming material-5 was obtained in the same manner as the image forming material-1 except that the parts were replaced by parts by weight.

The polytetrafluoroethylene of the overcoat layer composition was converted to α-alumina (average particle size = 0.15 μm).
m) An image forming material-6 was obtained in the same manner as the image forming material-1 except that the amount was changed to 2 parts by weight.

The image forming material was the same as the image forming material-1 except that the polytetrafluoroethylene of the overcoat layer composition was replaced by 2 parts by weight of carbon black (Sevacarb MT, manufactured by Colombian Carbon Japan Co., Ltd.). -7 was obtained.

The polytetrafluoroethylene of the overcoat layer composition was converted to molybdenum disulfide (average particle size = 0.3
0 μm) Image forming material-1 except that it was replaced by 2 parts by weight
In the same manner as in the above, an image forming material-8 was obtained.

Comparative image forming material was prepared in the same manner as image forming material 1 except that the binder composition was changed as follows.
1 was obtained.

Polyurethane resin 10 parts by weight (Toyobo Co., Ltd., UR-8300 Tg: 23 ° C.) Polyester resin 3 parts by weight (Toyobo Co., Ltd., Byron V280 Tg: 72 ° C.) Phenoxy resin 2 parts by weight ( (PHKHH Tg: 100 ° C., manufactured by Phenoxy Associates, Inc.) Comparative image forming material-2 was obtained in the same manner as image forming material-1 except that the binder composition was changed as follows.

Polyurethane resin 10 parts by weight (Toyobo Co., Ltd., UR-8200 Tg: 73 ° C.) Polyester resin 3 parts by weight (Toyobo Co., Ltd., Byron V200 Tg: 67 ° C.) Phenoxy resin 2 parts by weight ( (Phenoxy Associates, Inc., PKHH Tg: 100 ° C.) Comparative image forming material-3 was obtained in the same manner as image forming material-1, except that the binder composition was changed as follows.

Polyurethane resin 10 parts by weight (Toyobo Co., Ltd., UR-8300 Tg: 23 ° C.) Polyester resin 3 parts by weight (Toyobo Co., Ltd., Byron V200 Tg: 67 ° C.) Phenoxy resin 2 parts by weight ( (PHKHH Tg: 100 ° C., manufactured by Phenoxy Associates, Inc.) Comparative image forming material-4 was obtained in the same manner as image forming material-1 except that the binder composition was changed as follows.

Polyurethane resin 6 parts by weight Polyester resin 7 parts by weight Phenoxy resin 2 parts by weight Comparative image forming material-5 was obtained in the same manner as image forming material-1 except that the binder composition was changed as follows.

Polyurethane resin 8 parts by weight Polyester resin 3 parts by weight Phenoxy resin 4 parts by weight Comparative image forming material-6 was obtained in the same manner as image forming material-1 except that the binder composition was changed as follows.

Polyurethane resin 4 parts by weight Polyester resin 5 parts by weight Phenoxy resin 6 parts by weight Comparative image forming material-7 was obtained in the same manner as image forming material-1 except that the binder composition was changed as follows.

Polyurethane resin 5 parts by weight Polyester resin 3 parts by weight Phenoxy resin 1 part by weight Comparative image forming material-8 was obtained in the same manner as image forming material-1 except that the binder composition was changed as follows.

Polyurethane resin 20 parts by weight Polyester resin 8 parts by weight Phenoxy resin 4 parts by weight Comparative image forming material-9 in the same manner as image forming material-1 except that polytetrafluoroethylene of the coloring material layer composition was deleted. I got

Comparative image forming material-10 was obtained in the same manner as image forming material-1 except that polytetrafluoroethylene in the overcoat layer composition was omitted.

Comparative image forming material-11 was obtained in the same manner as image forming material-1, except that polytetrafluoroethylene was omitted from the coloring material layer composition and the overcoat layer composition.

Comparative image forming material-12 was obtained in the same manner as image forming material-1 except that the polytetrafluoroethylene of the coloring material layer composition was changed to 0.4 part by weight.

Comparative image forming material-13 was obtained in the same manner as image forming material-1, except that the polytetrafluoroethylene of the coloring material layer composition was changed to 22 parts by weight.

Comparative image forming material-14 was obtained in the same manner as image forming material-1, except that the polytetrafluoroethylene in the overcoat layer composition was changed to 0.4 part by weight.

Image forming material except that the polytetrafluoroethylene of the overcoat layer composition was changed to 11 parts by weight.
In the same manner as in Example 1, Comparative Image Forming Material-15 was obtained.

As a release sheet, a 25 μm polyethylene terephthalate film (T-100 manufactured by Diafoil Hoechst Co., Ltd.) was used, and a coating liquid for forming an adhesive layer having the following composition was applied on the film and dried to a thickness of 5 μm. .0
A μm adhesive layer was formed. Next, the adhesive layer surface and the image forming layer surface of the release sheet with the adhesive layer are opposed to each other, and heated by a pressure heat roll (temperature: 95 ° C., transport speed: 30 mm / sec, pressure: 2.0 kg / cm) so that air bubbles do not enter. Then, pressure treatment was performed to obtain an integrated image forming material.

Polyurethane resin 5 parts by weight (Nipporan 3116, manufactured by Nippon Polyurethane Industry Co., Ltd.) Methyl ethyl ketone 50 parts by weight Toluene 45 parts by weight (Evaluation of pinhole) A sample (16 cm × 100 cm) in which only the colorant layer was applied and calendered ), A 2.0 kg weight was hung on the end, wound around a guide roll at an angle of 90 ° C., and reciprocated 10 times, and evaluated according to the following four grades. Samples are 5 pieces each, 100 μm to 300
The average number (P) of μm pinholes was expressed in terms of 1.0 m ² .

4: P ≦ 10 3: 10 <P ≦ 30 2: 30 <P ≦ 100 1: 100 <P (Evaluation of abrasion property) Using an unexposed sample coated up to the overcoat layer, tribogear HEIDON TYPE
It measured using 14DR (made by Shinto Kagaku). The sample was fixed to a measurement table, fixed to a table so that the OC surface and the 30 mm flat indenter were in contact with each other, a load of 1 kg was applied to the indenter and reciprocated 20 times at a distance of 10 cm, and the degree of scratching was evaluated in four steps. .

4: No scratch 3: 1 to 2 scratches 2: several scratches 1: whole scratch Semiconductor laser (LT090MD, manufactured by Sharp Corporation)
Using a main wavelength of 830 nm, the image was exposed by focusing on the surface of the image forming layer and performing scanning exposure from the support side. Next, peel off the release sheet of the image forming material,
An image was formed. Sensitivity and resolution of the formed image,
The following criteria were used to evaluate the sensitivity, stain on the solid exposed portion, and abrasion.

(Evaluation of sensitivity) 0.5 m at a beam diameter of 4 μm
Solid scanning exposure to form mx 0.5mm image
The average exposure of the surface of the image forming material on which the image is formed
Amount (E: mJ / cm ^Two) Was evaluated on a 4-point scale.

4: E ≦ 100 3: 100 <E ≦ 250 2: 250 <E ≦ 400 1: 400 <E (Evaluation of resolution) Average exposure of the surface of the image forming material at a beam diameter of 4 μm and a scanning pitch of 4 μm The number (N) of lines that can be confirmed per 1 mm when forming an image with the amount is 4
It was evaluated on a scale.

4: 125 = N 3: 120 ≦ N <125 2: 110 ≦ N <120 1: 110> N (Evaluation of contamination on solid exposed portion) 10 mm × 4 μm beam diameter
After performing a solid scanning exposure of 10 mm and removing the release sheet,
Optical densitometer (X-lite 31 manufactured by X-rite)
In 0), the visual density (OD) was measured, and the density of the support was subtracted, and evaluated on a 4-point scale.

4: 0.001 ≧ OD 3: 0.005 ≦ OD <0.0012 2: 0.01 ≦ OD <0.0051 1: 0.03 ≦ OD <0.01 In all cases, the judgment was 3 or more. Those passed.

Table 1 shows the constitution of each image forming material, and Table 2 shows the results.

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[Table 1]

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[Table 2]

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As demonstrated in the examples, according to the present invention, a high-density, high-resolution image can be obtained, no pinholes occur in the manufacturing process, and scratches hardly occur after image formation. A forming material can be obtained.

Claims (3)

[Claims] 1. A support having at least a color material layer on a support, wherein the color material layer contains a polyurethane resin (B1), a polyester resin (B2) and a phenoxy resin (B3) as binders. An image forming material, wherein each of B1 and B2 has a glass transition temperature (Tg) of 70 ° C. or more. 2. The binder is contained in a relation of B1> B2 and B1> B3 by weight, and its content is 10 to 3 with respect to all coloring agents and inorganic compounds contained in the coloring material layer.
The image forming material according to claim 1, wherein the content is 0% by weight. 3. A support having at least a color material layer and an overcoat layer on a support, wherein carbon black, an inorganic filler,
One or more materials selected from polytetrafluoroethylene and molybdenum disulfide are used in the overcoat layer in an amount of 0.5 to 10% by weight based on the total solid content, and in the color material layer in an amount of 0.5 to 10% by weight based on the colorant. An image forming material, which is contained at 10.0% by weight.