JP2000255167A - Image forming material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming material which provides an image having a high resolution and strong resistance to scratching while prominent in the dispersing stability of a coloring material, whose productivity is improved, and an image forming method using the material. SOLUTION: An image forming material is constituted of an image forming layer and a protecting layer, which are laminated on a substrate in the sequence, while the image forming layer consists of a coloring material, capable of absorbing light having the wavelength of exposing light source and dispersed in a resin binder while causing abrasion by the exposure of high-density energy light. In such an image forming material, the resin binder of the image forming layer contains brominated phenoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a high-density image, a high-resolution image with a small amount of residual color and minute stains on an ablation portion, and a high scratch resistance. The present invention also relates to an image forming material having excellent colorant dispersion stability and improved productivity, and an image forming method using the same.

[0002]

2. Description of the Related Art Hitherto, there has been known a recording method in which light energy such as a laser beam is focused and irradiated onto 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). And
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.

For example, JP-A-8-334894, JP-A-8-337053 to JP-A-8-337056 and JP-A-9-15849 disclose that the residual ratio of an image forming layer is small due to ablation using a high-intensity laser beam. Further, a method and an image forming material for forming a high-density and high-resolution image are described.

[0004]

When the image forming method disclosed in the above patent is used, a high-density, high-resolution image with a small residual ratio of the image forming layer can be obtained. Also, Japanese Patent Application Laid-Open No.
By using a phenoxy resin described in, for example, No. 4894, the curing reaction with a crosslinking agent proceeds, and the scratch resistance of the image material is improved. However, there is a problem that the stability of the colorant dispersion liquid is poor and the production stability is deteriorated.

Accordingly, it is an object of the present invention to provide a high-density image with a sufficient density, little residual color and minute stains on the ablation portion, and a high scratch resistance of the obtained image material. An object of the present invention is to provide an image forming material having excellent dispersion stability of a coloring material and improved productivity, and an image forming method using the same.

[0006]

The above object of the present invention is achieved by the following constitution.

(1) An image forming layer and a protective layer are laminated on a support in this order. The image forming layer is formed by dispersing a colorant capable of absorbing light of a wavelength of an exposure light source in a resin binder, and forming a high density energy light. An image forming material which undergoes ablation upon exposure to light, wherein the resin binder of the image forming layer contains a brominated phenoxy resin.

(2) An image forming layer and a protective layer are laminated on a support in this order, and the image forming layer is formed by dispersing a colorant capable of absorbing the wavelength light of an exposure light source in a resin binder, and forming a high density energy light. in the image forming material to cause ablation by exposure of a resin binder modified phenoxy resin of the image forming layer, -SO ₃ is the modified phenoxy resin M, -OSO ₃ M, -COOM and -PO (OM
₁ ) ₂ (where M is a hydrogen atom or an alkali metal, M ₁
Represents a hydrogen atom, an alkali metal or an alkyl group. An image-forming material comprising a resin having at least one polar group selected from the group consisting of:

(3) The ablation type image forming material as described in (1) or (2) above, wherein the coloring material of the image forming material is a metal powder.

(4) The ablation-type image forming material as described in any one of (1) to (3) above, wherein a release sheet is laminated on the protective layer side of the image forming material.

(5) Using the image forming material as described in (4) above, performing image exposure with laser light from the transparent support side, ablating the image forming layer in the exposed portion, and peeling off the release sheet to form an image. An image forming method, wherein an exposed portion of a layer is transferred to a release sheet and removed.

(6) An image forming method, wherein the image forming material according to any one of the above items (1) to (4) is image-exposed using a laser having a wavelength of 600 to 1200 nm from a visible light to a near infrared region. .

Hereinafter, the present invention will be described in detail. In the image forming material of the present invention, an image forming layer and a protective layer are laminated on a support in that order, and in the image forming layer, a colorant capable of absorbing the wavelength light of an exposure light source is dispersed in a resin binder.

The resin binder of the present invention comprises the structural units of the following general formulas (1) to (4), but contains at least (2), (3) or (4).

[0015]

Embedded image

In the general formula (4), R represents —SO
₃ M, —OSO ₃ M, —COOM, —PO (OM ₁ ) ₂ (where M represents a hydrogen atom or an alkali metal, M ₁ represents a hydrogen atom, an alkali metal or an alkyl group, and X represents a hydrogen atom Or a bromine atom.) In such a binder resin, the amount of bromine atoms in the phenoxy resin is preferably from 10 to 70% by weight. Also, -SO ₃
M, —OSO ₃ M, —COOM, or —PO (OM ₁ ) ₂ is present in an amount of 0.01 to 0.5 mmol / g of the phenoxy resin.
mmol is preferred. In addition, the resin of the present invention uses 1
When it is 00, 0.1 to 25 parts is preferable. Also,
It is preferable to use it with another resin.

Other resins include vinyl chloride resins such as polyurethane, polyester, and vinyl chloride copolymer;
Polyolefin resins such as butadiene-acrylonitrile copolymer, polyvinyl acetal resins such as polyvinyl butyral, cellulose resins such as nitrocellulose, styrene resins such as styrene-butadiene copolymer, acrylic resins such as polymethyl methacrylate, Examples include polyamide, phenolic resin, and other epoxy resins.

The binder resin may be used alone or in combination of two or more. The content of the entire binder resin is preferably 5 to 30 parts when the colorant powder is 100.

The support used in 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. Further, when the image forming method described later is carried out, the support is irradiated with high-density energy light from the support side. When performing image exposure,
The transmittance for the wavelength of the energy light is preferably 50% or more, and more preferably 70% or more. Further, titanium oxide within a range not to impair the effects of the present invention,
Fillers such as zinc oxide, barium sulfate and calcium carbonate, coloring agents, antistatic agents and the like may be added.

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

As the coloring material of the present invention, coloring material fine particles are preferably used. As the coloring material fine particles, fine particles having a color tone according to the intended use can be appropriately selected and used from conventionally known coloring material fine particles (hereinafter abbreviated as coloring material fine particles).

As the above-mentioned coloring material fine particles, coloring material fine particles which can efficiently ablate by converting laser light into heat are more preferable from the viewpoint of the stability of the coating solution during production and the cost. For example, to produce a black image such as a transparent manuscript or a medical diagnostic image when producing a printing plate, graphite, carbon black, metal nitride, metal carbide, metal boride, cobalt tetroxide, iron oxide, Coloring material fine particles such as chromium oxide, copper oxide, titanium black, and magnetic powder that absorb in the wavelength region of 600 to 1200 nm can be used. In particular, magnetic powder is used in view of image resolution and remaining concentration of ablated part. Is more preferred.

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 a ferromagnetic metal powder 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 has a major axis diameter of preferably 0.30 μm or less, more preferably 0.20 μm or less. By using such a ferromagnetic metal powder, the surface property of the image forming layer is improved. Can be done. Further, the content of the coloring material fine particles contained in the image forming layer described above,
It is about 50 to 99% by weight, preferably 60 to 95% by weight of the image forming layer forming component.

The image forming layer may contain additives such as a lubricant, a durability improver, a dispersant, an antistatic agent, a filler, a filler and a curing agent as long as the effects of the present invention are not impaired. Good.

Examples of the lubricant include fatty acids, fatty acid esters, fatty acid amides, (modified) silicone oils, (modified) silicone resins, fluororesins, and carbon fluorides. Can be mentioned. Examples of the dispersant include those described in paragraph No. 0093 of JP-A-4-214218, and examples of the antistatic agent include cationic surfactants, anionic surfactants, and nonionic surfactants. Agents, polymeric antistatic agents, conductive fine particles, etc., and “11290 Chemical Products”, Chemical Daily, p. 875
To 876 and the like.
Fillers include carbon black, graphite,
TiO ₂ , BaSO ₄ , ZnS, MgCO ₃ , CaCO ₃ ,
ZnO, CaO, WS ₂ , MoS ₂ , MgO, SnO ₂ ,
Al ₂ O ₃ , α-Fe ₂ O ₃ , α-FeOOH, SiC, C
eO ₂ , BN, SiN, MoC, BC, WC, titanium carbide, corundum, artificial diamond, garnet,
Examples include inorganic fillers such as garnet, silica stone, triboli, diatomaceous earth, and dolomite, and organic fillers such as polyethylene resin particles, fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles, and melamine resin particles.

The curing agent can be used without any particular limitation as long as it can be cured, but is preferably a curing agent containing mainly an isocyanate group, and further contains a carbodiimide group and an oxazoline group. Curing agents can be used.

By hardening the image forming layer by adding such a curing agent, not only the durability of the formed image is improved, but also the residual color of the image forming layer portion removed by the image forming method described later. Can be eliminated.

The amount of these additives is about 0 to 20% by weight, preferably 0 to 15% by weight.

The thickness of the image forming layer is 0.1 to 2.0 μm
And more preferably 0.2 to 1.2 μm. By setting the content in this range, in the image forming method described later, irradiation with low-energy high-density light
In other words, an image can be formed with high sensitivity. or,
The image forming layer may be formed as a single layer, or may be formed as multiple layers having the same or different compositions. In the case where the image forming layer is formed as a multilayer, it is more sensitive to include a photothermal conversion compound in the image forming layer near the support. It is preferable from the viewpoint.

Examples of the binder resin for the protective layer of the image forming material of the present invention include vinyl chloride resins such as polyurethane, polyester and vinyl chloride copolymers, and vinyl chloride resins such as vinyl chloride-vinyl acetate copolymer. Butadiene-
Polyolefin resin such as acrylonitrile copolymer,
Polyvinyl acetal resin such as polyvinyl butyral, cellulose resin such as nitrocellulose, styrene resin such as styrene-butadiene copolymer, acrylic resin such as polymethyl methacrylate, polyamide, phenol resin, epoxy resin, phenoxy resin, polyvinyl Acetal resins such as butyral, polyvinyl acetoacetal and polyvinyl formal, and water-soluble resins such as polyvinyl alcohol and gelatin.

The binder resin may be used alone or in combination of two or more.

It is preferable to add a curing agent such as polyisocyanate.

If necessary, the protective layer may contain the same lubricants, antistatic agents, durability improvers, fillers, fillers and the like as those which can be added to the image forming layer. The thickness of the protective layer is preferably from 0.03 to 30.0 μm, more preferably from 0.05 to 10 μm.

The image-forming material of the present invention may be used in accordance with the purpose, if antistatic, transporting or blocking prevention is required on the back surface of the support, in addition to the above-mentioned support and image forming layer. It is preferable to provide a backing layer, which may be coated with a commercially available backing layer-forming composition, or may be provided in advance on a support, and when newly provided, a known backing layer according to various purposes may be appropriately provided. It can be provided selectively.

Further, as long as the effects of the present invention are not impaired,
When the bonding force between the support and the image forming layer, the coating property of the image forming layer provided by coating or the antistatic of the image forming material, etc. are required, it is preferable to provide an intermediate layer or the like according to each purpose, Known intermediate layers for various purposes can be appropriately selected and provided.

The thickness of such an intermediate layer or backing layer is
The thickness is about 0.05 to 10 μm, preferably 0.1 to 5 μm.

In the image forming method of the present invention described below,
A release layer provided for transferring an image by peeling after image exposure is used as a release layer by forming a layer with a resin having self-supporting property or using a resin film used as a support as described above as a release layer. . An adhesive layer may be provided between the release layer and the image forming layer.

Such an adhesive layer may be any of those having adhesiveness at normal temperature by themselves and those exhibiting adhesiveness by applying heat or pressure. For example, a resin having a low softening point, an adhesiveness-imparting agent, It can be formed by appropriately selecting 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 that are solid at ordinary temperature and reversibly liquefy or soften when heated.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 phenol Rosin derivatives such as fats, phenolic resins, ketone resins, epoxy resins, diallyl phthalate resins, terpene hydrocarbon resins, cyclopentadiene resins, polyolefin resins, polycaprolactone resins, polyolefin oxides such as polyethylene glycol and polypropylene glycol, etc. And the like.

The thickness of the release layer is about 0.1 to 100 μm,
The thickness is preferably 0.5 to 50 μm, and the thickness of the adhesive layer is about 0.1 to 40 μm, preferably 0.3 to 30 μm.

In the present invention, an antistatic agent is added to any one of the above-mentioned support, image forming layer, backing layer, intermediate layer, release layer and adhesive layer for the purpose of preventing blocking and adhesion of dust. Is preferred. As such an antistatic agent, those added to the image forming layer can be appropriately selected and used.

The image forming layer is formed by kneading, for example, a colorant particle, a binder and, if necessary, a lubricant, a durability improver, a dispersant, an antistatic agent, a filler, a filler, a curing agent and a solvent. A high-concentration paint is prepared, and then the high-concentration paint is diluted to obtain a coating for application, applied on a support and dried to form a coating.

Solvents include alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve), aromatics (toluene, xylene, chlorobenzene, etc.), ketones (acetone, methyl ethyl ketone, etc.), and ester-based solvents. Use of solvents (such as ethyl acetate and butyl acetate), ethers (such as tetrahydrofuran and dioxane), halogen solvents (such as chloroform and dichlorobenzene), and amide solvents (such as dimethylformamide and N-methylpyrrolidone). Can be. Further, for kneading and dispersing the components of the image forming layer, 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 used.

The formation of the image forming layer on the support can be carried out, for example, by coating and drying with an extrusion-type extrusion coater. A calendering treatment may be performed to make the orientation of the magnetic powder particles uniform or to make the surface properties of the image forming layer uniform. Alternatively, the magnetic powder particles may be randomly oriented by performing a non-orientation treatment. Through these processes, a high-resolution image can be obtained.

When another layer is provided on the same side as the image forming layer in addition to the image forming layer, coating and drying may be repeated for each layer. It may be dried. In that case, reverse roll,
Gravure roll, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater,
Bar coater, transfer roll coater, kiss coater,
It can be applied by a combination of a cast coater or a spray coater and an extrusion coater.

In the multi-layer coating in the wet-on-wet method, the upper layer is coated while the lower layer is kept wet, so that the adhesion between the upper and lower layers is improved.

When the release layer is laminated on the image forming layer, if the release layer is a resin having a self-supporting property, the release layer forming resin is dissolved in a solvent and applied and dried in the same manner as the image forming layer. The layer forming resin may be melt-kneaded and provided on the image forming layer by extrusion lamination. When a resin film such as that used for a support is used as a release layer, a film having heat sealing properties such as polyethylene or polypropylene may be formed by laminating an image forming layer surface and a film and applying a heat roll. A release layer can be formed by heat and pressure using a hot stamp. When a film having no heat sealing property is used, an adhesive layer is provided on the image forming layer and the films are laminated. That is, the adhesive layer forming composition is applied and dried on the image forming layer to laminate the resin film, or the adhesive layer forming composition is applied and dried on the resin film, or the adhesive layer forming composition is heated and melted and extrusion lamination is performed. After that, the surface of the adhesive layer is superimposed on the image forming layer, and bonded by a heat and pressure treatment using a heat roll or a hot stamp to form a release layer. As the heat treatment, with a heat roll, room temperature to about 180 ° C., preferably 30 to 160 ° C.,
About 20 kg / cm, preferably 0.5 to 10 kg / cm
cm pressure, speed 1-200 mm / sec, preferably 5
This is performed while conveying at a speed of 100 mm / sec. When a hot stamp is used, the temperature is from room temperature to about 180 ° C., preferably 30 ° C.
At ~150 ℃, 0.05~10kg / cm ² or so, preferably at a pressure of 0.5 to 5 kg / cm ^2, 0.1 to 50
Heat for about seconds, preferably 0.5 to 20 seconds.

In the present invention, an image can be formed by the following four methods based on the above-described constitution of the image forming material.

-Image Forming Method 1- In the first image forming method, image exposure using high-density energy light is performed from the support side of an image forming material having an image forming layer containing metal atom-containing particles on a support, An image is formed by removing the image forming layer in the exposed portion.

The image forming layer used here may be composed of one layer, or may be composed of two or more layers. When it is composed of two or more layers, for example, an image forming layer in which a colorant-containing layer having an absorption at 350 to 600 nm is laminated on a photothermal conversion compound-containing layer having an absorption at at least 600 to 1200 nm is exemplified. Can be.

The high-density energy light used for image exposure from the support side can be used without particular limitation as long as it is a light source capable of removing the exposed portion by any method. Among them, in order to obtain high resolution, electromagnetic waves whose energy application area can be narrowed down, particularly ultraviolet rays, visible rays, and infrared rays having a wavelength of 1 nm to 1 mm are preferable. As a light source to which such high-density energy light can be applied, , For example a laser,
Examples include 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, and a high-pressure mercury lamp. The energy applied at this time can be appropriately selected by adjusting the exposure distance, time, and intensity according to the type of the image forming material.

In the case where the high-density energy light is subjected to batch exposure, a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be overlaid 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 controlled to be exposed by an optical shutter material such as a liquid crystal or PLZT, an image signal is used. It is possible to carry out the corresponding digital exposure. 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 squeezing light into a beam, and furthermore, by using a laser as a light source, it is easy to narrow the exposure area to a very small size, and it is possible to form a high-resolution image Formation is possible.

As the laser light source used in the present invention, generally well-known ruby lasers, YAG
Laser, glass laser and other solid lasers; He-N
Gas lasers such as e laser, Ar ion laser, Kr ion laser, CO ₂ laser, CO laser, He-Cd laser, N ₂ laser, excimer laser; InGaP laser, AlGaAs laser, Ga
Semiconductor lasers such as an AsP laser, an InGaAs laser, an InAsP laser, a CdSnP ₂ laser, and a GaSb laser; chemical lasers, dye lasers and the like; It is preferable to use a laser having a wavelength of 600 to 1200 nm in terms of sensitivity since light energy can be efficiently converted to heat energy. Further, among them, a laser of 750 to 1200 nm can efficiently convert light energy into heat energy.
It is more preferable in terms of sensitivity, and among them, it is particularly preferable to use a high illuminance laser as long as the laser has the same wavelength.

In the present invention, image formation is performed by exposing the image forming layer to high-density energy light after image exposure, and removing the exposed portion by any method. If the light exposure energy is sufficient to completely destroy and scatter the image forming layer, it can be removed by suctioning the scattered material, in which case it is adjacent to the image forming layer. By providing the suction portion at the portion where the heat is to be removed, the suction portion can be efficiently removed.

Further, when the exposure energy of the high-density energy light does not completely destroy the image forming layer, for example, when the bonding force between the support in the exposed portion and the image forming layer is reduced, the above-described case is adopted. In addition to the removal by suction, it can be removed by an image forming method 3 or 4 described later.

Here, the decrease in the bonding force means that the image forming layer is completely scattered due to a physical or chemical change.
This includes phenomena such that the image forming layer is partially destroyed and / or scattered, the surface of the image forming layer is not destroyed, and a physical or chemical change occurs only in the vicinity of the support.

-Image Forming Method 2- In the second method, an image forming material having an image forming layer containing at least metal atom-containing particles and a binder on a support is exposed to high-density energy light from the support side. The image forming is performed by reducing the bonding force between the support in the exposed portion and the image forming layer, and then removing the image forming layer in the exposed portion.

The image forming layer containing the metal atom-containing particles and the binder used in the present invention includes the above-described image forming layer,
Refers to an image forming layer containing only metal atom-containing particles that have absorption only at a wavelength of 350 nm or less as a colorant, and the high-density energy light and the removal method are the above-described image forming method 1 and image forming method 3 described below. Alternatively, it can be performed by selecting 4 as appropriate.

Further, the decrease in the bonding force referred to here also means that the image forming layer is completely scattered due to physical or chemical change.
This includes phenomena such as partial destruction and / or scattering of the image-forming layer, the surface of the image-forming layer not being destroyed, and physical or chemical changes occurring only in the vicinity of the support.

-Image Forming Method 3- In the third image forming method of the present invention, image exposure using high-density energy light from the support side is performed using the above-described image forming material having the image forming layer laminated on the support. To reduce the bonding strength between the exposed portion of the image forming layer and the support, and contact the image forming layer with the adhesive layer or the adhesive layer surface of an adhesive sheet having an adhesive layer or an adhesive layer on a substrate to form an image. An image is formed by transferring the exposed portion of the formation layer with the high-density energy light to the adhesive sheet side.

In the image forming method of the present invention, when the image forming layer is partially destroyed and / or scattered due to a physical or chemical change, the image remaining on the pressure-sensitive adhesive sheet to be described later is the same as in image forming methods 1 and 2. The exposed portion of the image forming layer may be removed by suction. When such suction removal is difficult, it is preferable to adjust the exposure energy of the high-density energy light so that a physical or chemical change occurs only in the vicinity of the support.

As the adhesive sheet in this case, a commercially available adhesive sheet, a heat sealing material or a laminate material can be used as it is. Further, in order to press or heat and pressure treatment with the image forming material and the adhesive sheet facing each other,
It can be used without particular limitation as long as it can be pressurized or heated and pressurized without increasing the adhesiveness and mixing of bubbles and the like.
When pressure is applied, a pressure roll, a stamper, or the like can be used, and when heat and pressure treatment is performed, 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 10 k / cm.
g / cm, and the conveying speed is usually 0.1 to 200.
mm / sec, preferably 0.5 to 100 mm / sec,
The pressure when using a stamper is usually 0.05
-10 kg / cm ² , preferably 0.5-5 kg / c
m ² , and the pressurization time are 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. The heating temperature when using a heat roll is usually 60 to 200 ° C, preferably 80 to 180 ° C.
° C, and the pressure is usually 0.1 to 20 kg / c.
m, 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. The temperature is usually in the range of 60 to 200 ° C., preferably 80 to 150 ° C., and the pressure is usually 0.
05 to 10 kg / cm ² , preferably 0.5 to ⁵ kg / cm ²
cm ² , and the heating time is generally 0.1 to 50 seconds, preferably 0.5 to 20 seconds.

The method of peeling may affect image formation, such as a method of fixing a peeling angle using a peeling plate or a peeling roll, or a manual peeling method of peeling off an adhesive sheet and an image forming material without fixing them by hand. If not, various peeling methods can be used.

In the above description, an image forming material having a single image forming layer provided on a support has been described. However, when the image forming layer is composed of two or more layers, the same applies to the above case. The bonding force between the support and the image forming layer adjacent to the support may be reduced, or when a plurality of image forming layers having different compositions are provided on the support, for example, a photothermal conversion compound is contained as a colorant. A first image forming layer, and 35
When the second image forming layer containing a compound having an absorption in the wavelength range of 0 to 1200 nm is provided in this order, the position for reducing the bonding force may be between the support and the first image forming layer. It may be between the first image forming layer and the second image forming layer. Further, an intermediate layer may be provided between the image forming layer and the support.

-Image Forming Method 4- In the fourth image forming method, image exposure with high-density energy light is performed from the support side using the above-described image forming material having the release layer laminated on the image forming layer. Reduce the bonding force between the support of the exposed portion of the image forming layer and the image forming layer,
The image forming is performed by transferring a portion of the image forming layer exposed to the high-density energy light to the release layer side by peeling the release layer.

In this method, the above-described image forming methods 1 and 2
In the case of (3), at the time of image exposure with high-density energy light, scattering of the image forming layer may occur depending on the exposure conditions, but since the release layer is laminated on the image forming layer of the image forming material, The image can be formed without such scattering.

In this image forming method, the image forming material used is a case where the release layer and the image forming layer are bonded in advance,
In some cases, the release layer and the image forming layer are not adhered just because they are in close contact, and in the latter case, the composition of the adhesive layer,
Partial adhesion between the adhesive layer and the image forming layer, the adhesive layer contains a filler, etc., so that a minute gap is provided between the adhesive layer and the image forming layer, and heat conduction and support from the image forming layer By designing so as not to hinder the deformation of the image forming layer due to the decrease in the bonding force between the body and the image forming layer, it is possible to reduce the bonding force between the support and the image forming layer at the same time as the image exposure with high density energy light. The part where the bonding force between the support of the image-exposed portion and the image-forming layer is reduced as it is adhered to the adhesive layer due to the generated heat and scattering, and the image is formed simply by peeling off, and after the image exposure After the image forming material is heated and pressurized, the release layer is peeled off, and a portion of the image forming layer in which the bonding force between the support and the image forming layer is reduced may be transferred to the release layer side.

In this method, when the image is exposed with high-density energy light in the case of the image forming method 1, 2 or 3, the image forming layer may be scattered depending on the exposure conditions. Since the release layer is laminated on the formation layer, the image can be formed without such scattering.

The image exposure with high-density energy light can be performed in the same manner as in the image forming method 1. The method of peeling off the image forming material and the release layer is also the same as the method of image forming method 3.
The method of peeling off the image forming material and the adhesive sheet can be used as it is.

[0077]

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 <Image forming material>-Support-A transparent polyethylene terephthalate film (T-60, manufactured by Toray Industries, Inc.) having a thickness of 100 µm, on which the image forming layer laminated surface was subjected to corona discharge treatment.

-Image Forming Layer- The following composition is kneaded and dispersed using a kneader and a sand mill to prepare an image forming layer forming coating solution containing metal atom-containing particles, and is applied on a support by extrusion coating. Then, after drying, a calender treatment was performed at a pressure of 150 kg / cm to form an image forming layer having a thickness of 0.9 μm. After further aging at 60 ° C. for 120 hours, Table 1
Was formed. Further, a protective layer having a dry thickness of 0.3 μm was applied on the image forming layer and dried.
Aging was performed for 0 hour to produce an image forming material.

Metal powder [manufactured by Kanto Denka Kogyo Co., Ltd., MAP T1650SB] 100 parts Polyester-modified polyurethane resin [Toyobo Co., Ltd., Byron UR-4122] 10 parts Phenoxy resin of the present invention (described in Table 1) 5 parts Alumina [High-purity alumina HIT6, manufactured by Sumitomo Chemical Co., Ltd.] 5 parts Phosphate ester [Phosphanol RE610, manufactured by Toho Chemical Industry Co., Ltd.] 3 parts Isocyanate-based curing agent [Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.] 1 part Cyclohexanone 100 parts Methyl ethyl ketone 100 parts Toluene 100 parts The phenoxy resin of the present invention used above was synthesized by the following method. In Table 1, the sample No. Sample Nos. 1 to 9 were each made of a phenoxy resin (PKHH, manufactured by Union Carbide). 10 to 14 are obtained by heating and dissolving 100 parts of a brominated phenoxy resin (8024, manufactured by Asahi Ciba, 25% by weight of bromine) as a phenoxy resin in 500 parts of anone or dimethylformamide.
0.2 parts of pyridine or triethylamine or trimethylammonium chloride were added. Further, after diluting with 200 parts of toluene or dimethylformamide, the polar group is added with 0.1 part of dibutyl phosphate, chloroethanesulfonic acid, chlorosulfuric acid or monochloroacetic acid.
5 to 10 parts were added, and the mixture was introduced with heating and stirring for 2 to 5 hours. Table 1 shows the content of the introduced polar group.

-Protective layer- The following composition was applied with a wire bar after the colorant layer was hardened,
Subsequently, it was dried to form a protective layer having a thickness of 0.25 μm.

Phenoxy resin [PKHH, manufactured by Union Carbide Co., Ltd.] 5.9 parts Silica fine particles [E-743, manufactured by Nippon Silica Industry Co., Ltd.] 0.1 parts Polyethylene wax [T-15P manufactured by Gifu Shellac Co., Ltd.] -2] 0.5 parts Silicone resin [SP203V, manufactured by Dainichi Seika Kogyo Co., Ltd.] 0.5 parts Curing agent [Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.] 3.0 parts Cyclohexanone 150 parts Toluene 150 parts- Release layer (transfer object)-36 μm transparent polyethylene terephthalate film as a support [T-100 manufactured by Diafoil Hoechst Co., Ltd.]
E], a coating liquid for forming an adhesive layer having the following composition was applied and dried to form an adhesive layer having a thickness of 0.4 μm. Then, the surface of the adhesive layer of the release layer with the adhesive layer (transfer member) and the surface of the protective layer of the image forming material are faced to each other, and a heating / pressing roll (conveying speed;
(kg / cm ² ) to form an image forming material in which an image forming layer, a protective layer, and a release layer are laminated in this order on a support by heating and pressurizing so as to prevent bubbles from entering.

Polyurethane resin [Nipporan 3116, manufactured by Nippon Polyurethane Industry Co., Ltd.] 5 parts Methyl ethyl ketone 50 parts Toluene 45 parts <Image forming method> A semiconductor laser (manufactured by Dainippon Screen Mfg. Co., Ltd .: TCP-1080, main wavelength 830 nm) is used. The image is formed by focusing on the surface of the image forming layer, scanning and exposing with an energy of 300 mJ / cm ² from the side of the image forming layer support, and exposing the unnecessary image forming layer in the exposed portion to the release layer. did.

Evaluation of Stain on Exposed Area (Dmin) A halftone image of 0% 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 determined. , Any 30 points can be measured with a densitometer [X
-Rite: X-rite 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- Using a device capable of reciprocating at a constant speed by applying a load by facing the protective layer surfaces on which no image is formed, the area where the halftone dot image and the protective layer surface are in contact with each other is 1 cm. After applying a load of 1000 g / cm ^{2 in} a width of 2 cm (width direction is 1 cm) and reciprocating 20 times at a conveying speed of 100 cm / sec, observe the rubbed surface to determine the degree of scratching according to the following criteria. Was evaluated.

：: 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. ×: A scratch reaching the image forming layer is observed. ×: A halftone dot image is observed with transmitted light, and a transmitted scratch is observed.

—Stability of Coating Solution— The coating solution for the image forming layer was collected in a 50 ml sample bottle, and the container was sealed and allowed to stand. After 24 hours, the supernatant was
Was applied on glass with an applicator and observed.

A: Observation of the sample and surface gloss and transmission density are almost the same as the initial values (within 5%) O: Observation of the sample and either surface gloss or transmission density fluctuates slightly from the initial value (within 10%) Δ: Both surface gloss and transmission density fluctuate from the beginning when the sample is observed (within 10%). ×: Both surface gloss and transmission density fluctuate from the beginning when the sample is observed (10% or more). The results are shown in Table 1.

[0090]

[Table 1]

From Table 1, it can be seen that when the resin of the present invention is used, D
min, abrasion resistance and stability of the coating solution are improved.

[0092]

According to the present invention, a high-resolution image can be obtained, the obtained image material has high abrasion resistance, and the colorant has excellent dispersion stability and the productivity is improved. An image forming method can be provided.

Claims (6)

[Claims] 1. An image forming layer and a protective layer are laminated on a support in this order. The image forming layer is formed by dispersing a colorant capable of absorbing wavelength light of an exposure light source in a resin binder, and forming a high density energy light. An image forming material which undergoes ablation upon exposure, wherein the resin binder of the image forming layer contains a brominated phenoxy resin. 2. An image forming layer and a protective layer are laminated on a support in this order. The image forming layer is formed by dispersing a colorant capable of absorbing the wavelength light of an exposure light source in a resin binder, and forming a high density energy light. In an image forming material that undergoes ablation upon exposure, the resin binder of the image forming layer is a modified phenoxy resin, and the modified phenoxy resin is -SO
₃ M, -OSO ₃ 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), and is a resin having at least one polar group selected from the group consisting of: material. 3. The ablation type image forming material according to claim 1, wherein the color material of the image forming material is a metal powder. 4. The ablation-type image forming material according to claim 1, wherein a release sheet is laminated on the protective layer side of the image forming material. 5. An image forming material according to claim 4,
After performing image exposure with laser light from the transparent support side, ablating the image forming layer in the exposed portion, and then peeling off the release sheet, the exposed portion of the image forming layer is transferred to the release sheet and removed. Image forming method. 6. An image forming method, wherein the image forming material according to claim 1 is image-exposed using a laser having a wavelength of from 600 to 1200 nm in the visible to near infrared region. .