JPH11198532A - Method for forming image and image recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method for forming an image for incorporating a density gradation in the image having a binary image density, and an image recording medium having the density gradation formed by the method. SOLUTION: The method for forming an image comprises the steps of exposing an image forming material having at least one thermally active image forming layer on a first support, an image forming layer containing at least one porous or particulate image forming substance adjacent on the thermally active image forming layer and having at least one adhesive layer and a second support on these layers through the support, strengthening an adhesive strength between the thermally active image forming layer and the image forming layer of an exposed part, then releasing between the thermally active image forming layer and the image forming layer, separating it into a layer having a first region having an image forming substance and a second region having no image forming substance and an image material having the adhesive layer and the second support, then laminating a protective layer on the image material, thereby incorporating a density gradation in a boundary between the first region and the second region.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming method for giving an image having binary image densities a density gradation, and an image recording medium having the density gradation formed by the method.

[0002]

2. Description of the Related Art Conventionally, there has been known an image forming method in which light energy such as a laser beam is focused to remove only an exposed portion. 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 removing only the light irradiation part. It is used as a material, a transmission image at the time of medical diagnosis, or a transmission original at the time of producing a printing plate.

[0003] Of these, JP-A-2-501552 and the like disclose a layer of a porous or granular image-forming substance on a heat-active image forming surface on a first support, and a second support. By using a material on which is laminated, light energy such as a laser beam is focused and exposed from the direction of the first support, and then the first support and the second support are peeled off. An image forming method has been proposed in which a layer of a quality or granular image forming substance is formed on a first support, and the unexposed layer is formed on a second support.

[0004]

The image formed on the second support by the above-described image forming method is inferior in image durability since it is formed of a layer of a porous or granular image forming substance. I was In order to improve these disadvantages, Japanese Patent Application Laid-Open Nos. 5-504008 and 9-502670 disclose the second type.
It has been proposed that an image formed on a support is laminated with a protective layer to impart image durability.

[0005] On the other hand, when it is intended to be used for a transmission image or the like at the time of medical diagnosis, a density gradation is required, and with these image forming materials, visual unevenness is conspicuous depending on the exposure apparatus. As a means for solving these problems, a method of reducing the converging diameter of light energy such as a laser beam can be considered. , Or the exposure time is long, so it has not been realized yet.

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 method for giving an image having binary image densities a density gradation, and to have a density gradation formed by the method. An image recording medium is provided.

[0007]

The above objects of the present invention have been attained by the following constitutions.

(1) At least one heat-active image forming layer is provided on a first support, and at least one layer of a porous or granular image-forming substance adjacent to the heat-active image forming layer is provided. An image forming material having an image forming layer containing at least one adhesive layer and a second support on these layers, and exposing through a support to the heat-active image forming layer in an exposed portion. After enhancing the adhesion between the thermoactive image forming layer and the image forming layer, the first region having the image forming material and the second region having no image forming material are separated. After separating into a layer having a region and an image material having the adhesive layer and the second support, a protective layer is laminated on the image material, so that the density at the boundary between the first region and the second region is increased. An image forming method characterized by giving a gradation.

(2) The method of forming an image according to (1), wherein the method of laminating a protective layer on the image material after separation into the image material comprises transferring the protective layer by heating and / or pressing to laminate the protective layer. Method.

(3) The image forming method according to (1) or (2), wherein the exposure is exposure with high-density energy light.

(4) The image forming method as described in any one of (1) to (3) above, wherein the first region having the image forming substance contains a dye.

(5) The image forming method according to (4), wherein the dye according to (4) is a dye capable of chelating at least two sites with a metal ion, and the protective layer contains a metal ion supply compound.

(6) The image forming apparatus as described in any one of (1) to (3) above, wherein the first region having the image forming substance contains a color developer and the protective layer contains a color former. Method.

(7) The image forming apparatus as described in any one of (1) to (3) above, wherein the first region having the image forming substance contains a color former and the protective layer contains a developer. Method.

(8) The image forming apparatus as described in (6) or (7) above, wherein the color former is a silver source, and the developer is a reducing agent capable of reducing the silver source to a silver image. Method.

(9) An image recording medium wherein an image having a density gradation is formed at a boundary between the first area and the second area by the image forming method described in any one of 1 to 8 above.

Hereinafter, the present invention will be described in detail.

<Image Forming Method> First, an image forming material used in the image forming method of the present invention will be described. As shown in FIG. 1, the image forming material of the present invention comprises a first support 1, a stress absorbing layer 2, a thermally activated image forming layer 3, a porous or granular image forming layer 4, a release layer 5, a first A material laminated in the order of the adhesive layer 6, the second adhesive layer 7, and the second support 8,
Hereinafter, each layer will be described in detail.

As the first support 1 and the second support 8, acrylate, methacrylate, 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 resin films obtained by laminating two or more layers of the resin. it can.

In the present invention, the support is preferably stretched into a film and heat-set, from the viewpoint of dimensional stability. In the present invention, when performing the image forming method described below,
Since the condensed laser light is imagewise exposed from the support side, a support having a high transmittance to the effective wavelength of the laser light is preferable, and usually a support having a transmittance of 50% or more, more preferably 80% or more. It is preferable to use Note that a filler such as titanium oxide, zinc oxide, barium sulfate, or calcium carbonate may be added as long as the effects of the present invention are not impaired.
The thickness of the support is about 10 to 500 μm, preferably 1 to 500 μm.
5 to 250 μm.

The stress absorbing layer 2 is not particularly limited as long as it is a layer capable of absorbing physical stress, and may be an olefin resin, a PVC resin, an acrylic resin, a urethane resin, a polyester resin, a rubber resin, or the like. It can be formed of a layer mainly composed of an extensible resin or a resin having an elastic modulus, as described in JP-T-5-503899. The stress absorbing layer 2 is formed of a first adhesive layer 6 used.
And / or when the second adhesive layer 7 or the like can sufficiently cope with stress.

The thickness of the stress absorbing layer 2 is usually 0.5 to
It is 10 μm, preferably 1 to 5 μm.

The heat-active image forming layer 3 is a layer involved in image formation, and can be heat-activated by exposing the image forming material to high-density energy light. Then, the thermally active image forming layer 3
When exposed to high-density energy light and cooled rapidly,
The exposed parts adhere firmly to the porous or granular imaging layer 4. The heat-active image forming layer 3 is preferably formed of a layer mainly composed of the stress absorbing layer 2 or a resin having a softening temperature lower than the softening temperature of the first support 1. A resin, a polyvinyl acetal resin, an acrylic resin, a polyolefin resin, a polyester resin, a vinyl chloride resin, or a compound described in JP-A-5-503899 can be appropriately selected and used.

The heat-active image forming layer 3 may contain various additives within a range not to impair the object of the present invention. Examples of such additives include a light-to-heat conversion material, a filler, a lubricant, Examples include a imparting agent, a plasticizer, and an antistatic agent.

Incidentally, even when the stress absorption layer 2 is not provided, the same layer can be formed.
Is 0.05 to 10 μm, preferably 0.1 to 5 μm.

The porous or granular image forming layer 4 is composed of a porous or granular substance and a binder resin. If necessary, a pigment or dye of a desired color and a high density energy light are efficiently absorbed. A light-to-heat conversion material may be added.

[0027] Such porous or particulate materials include carbon black, graphite, phthalocyanine pigments and other known color pigments.
In addition, these porous or granular substances are usually 0.01
Those having an average diameter of from 10 to 10 μm are preferred, and more preferably from 0.01 to 5 μm.

Gelatin as a binder resin,
Examples thereof include poly (vinyl alcohol), hydroxyethylcellulose, gum arabic, methylcellulose, polyvinylpyrrolidone, polyethyloxazoline, polystyrene latex, and poly (styrene-maleic anhydride), and the weight ratio of pigment to binder resin is 4
It can be appropriately selected and prepared in the range of 0: 1 to 1: 2.

As the pigment or dye, a known pigment and / or dye having a desired color can be appropriately selected and used, and as the light-to-heat converting substance that absorbs high-density energy light, cyanine dye, rhodocyanine dye, Oxonol dye, carbocyanine dye, dicarbocyanine dye,
Tricarbocyanine dye, tetracarbocyanine dye,
Pentacarbocyanine dyes, styryl dyes, pyrylium dyes, phthalocyanine dyes, organic compounds such as gold-containing dyes,
Inorganic compounds such as graphite, carbon black, metal nitride, metal carbide, metal boride, cobalt trioxide, iron oxide, chromium oxide, copper oxide, titanium black, magnetic powder and the like can be mentioned.

Further, various additives can be added to the porous or granular image forming layer 4 as long as the object of the present invention is not impaired. Examples of such additives include a dispersant, a filler, and a lubricant. The adhesive force between the release layer 5 and the porous or granular image forming layer 4, which can include an agent, an antistatic agent, etc., is the adhesive force between the porous or granular image forming layer 4 and the thermally active image forming layer 3. The unexposed areas are designed to be peeled between the porous or granular image forming layer 4 and the thermally activated image forming layer 3. Note that the peeling position of the exposed portion may be the interface between the porous or granular image forming layer 4 and the peeling layer 5 or the cohesive failure of the peeling layer 5.

The release layer 5 can be formed from a wax, a wax-like compound or a resin-like compound.
Wax-like compounds such as polyethylene wax, carnauba wax, beeswax, paraffin wax, poly (vinyl stearate), poly (ethylene sebacate), sucrose polyester, polyalkylene oxide and dimethyl glycol phthalate, poly (methyl methacrylate) and A polymer or resinous compound such as a copolymer of methyl methacrylate and a monomer copolymerizable therewith can be used. Further, depending on the constitution of each layer described above, it may be used in combination as a binder resin such as poly (vinyl alcohol), gelatin or hydroxyethyl cellulose.

By using a resinous compound which is further applied as latex, the release layer 5
It is preferable to use such a latex because it can control the cohesive force. When such a latex is used, it is preferable to use an acrylic resin. , Clay particles and a filler such as polytetrafluoroethylene.

Various adhesive resins can be used for the first and second adhesive layers 6 and 7 as long as the object of the present invention is not hindered.
In the case where the image forming material is produced by laminating between the first adhesive layer and the second adhesive layer, the first and / or second adhesive layer can be adhered at the time of pressure treatment or heat / pressure treatment. It is composed of a resin layer. In the case where the adhesive layer is cured and bonded by an active energy ray such as ultraviolet curing, the first and / or the second adhesive layer is preferably formed of a composition curable by the active energy ray.

The resin that can be adhered during the pressure treatment or the heat and pressure treatment includes styrene resin, polyvinyl acetal resin, acrylic resin, polyolefin resin, polyester resin, vinyl chloride resin, epoxy resin and the like. Transition temperature of -50 to 60C, preferably -4
It is preferable to use a resin at 0 to 50 ° C.

As the compound which cures with an active energy ray, a conventionally known compound having an ethylenically unsaturated double bond or a combination of a compound having an epoxy group and a polymerization initiator may be appropriately selected and used. it can.

As the polymerizable compound having an ethylenically unsaturated bond, a known monomer capable of addition polymerization or cross-linking polymerization can be used without any particular limitation. Specific examples of the monomer include monofunctional (meth) acrylates And its derivatives, bifunctional (meth) acrylic esters and derivatives thereof, polyfunctional (meth) acrylic esters and derivatives thereof, and furthermore, acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to improve photopolymerizability. A so-called applied prepolymer can also be suitably used. In addition, "Chemical products of 11290", Chemical Daily, 286-2
Compounds described on page 94, compounds described in “UV / EB Curing Handbook (Raw Materials Edition)”, Polymer Publishing Association, pp. 11-65, and the like can also be suitably used.

Examples of the polymerization initiator include benzoin compounds such as benzoin, carbonyl compounds such as Michler's ketone, azo compounds such as azobisisobutyronitrile, sulfur compounds such as dibenzothiazolyl sulfide, and halogen compounds such as tribromophenyl sulfone. And various metal complexes such as metal carbonyl and titanocene, and a sensitizer may be added as necessary.

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 a polycondensate of a compound having a hydroxyl group and epichlorohydrin, a glycidyl-modified compound, and the like.
The compounds described on pages 778 to 787 can also be suitably used.

As the polymerization initiator, an amine compound (eg, ammonia, ethylenediamine, diethylenetriamine, phenylenediamine, etc.) upon receiving an active energy ray
(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.

Examples of such an acid generator include an s-triazine compound substituted with a trihalomethyl group, an iron arene complex, an onium salt, an aryldiazonium salt, a diazoketone, an o-nitrobenzyl ester, a sulfonic acid ester, a disulfone derivative, Examples include an imidosulfonate derivative, a silanol-aluminum complex, and the like.

The first adhesive layer 6 may be omitted if sufficient adhesion and adhesion can be obtained when the second adhesive layer 7 and the release layer 5 are bonded together.

The thickness of the first adhesive layer 6 and the second adhesive layer 7 is usually 0.5 to 50 μm, preferably 1 to 20 μm.
m.

In the present invention, the support comprises a plurality of first regions where the porous or granular image forming substance is adhered on the support, and a plurality of second regions where the support does not contain the image forming material. It is characterized in that a certain additive is contained in order to give a density gradation at the boundary between the plurality of first regions and the plurality of second regions of the binary image.

As an additive for forming such a density gradation, a dye or a developer or a color former can be used in a plurality of first areas where a porous or granular image forming substance is adhered on a support. Agents.

As the dye to be added to the porous or granular image-forming substance-containing layer, conventionally used heat diffusion dyes can be used as they are, and such dyes include methine dyes and azo dyes. Dyes, quinophthalone dyes, anthrisothiazole dyes, anthraquinone dyes, azomethine dyes, naphthoquinone dyes, indoaniline dyes and the like can be mentioned.

Further, when a compound containing a metal ion supply compound is contained in the protective layer described later, a dye capable of chelating at least two sites with a metal ion is used, which results in a shift in density gradation over time. It is preferable because it is reduced. Examples of such dyes include, for example, JP-A-4-82786, JP-A-4-164688, JP-A-4-164689, and 4-1.
No. 64690, No. 4-176686, No. 4-2350
No. 93, No. 4-292988, No. 4-320893
Nos. 4-34893, 5-177958, 4-62092, 4-65294, 4-73
No. 191, No. 4-82784, No. 4-94974,
4-97894, 4-232785, 4-2
69589, 4-339694, 5-1654
No. 5, No. 5-1855751, No. 4-62094,
4-65293, 4-78584, 4-82
No. 784, No. 4-82785, No. 4-82787,
4-89288, 4-89289, 4-15
No. 8092, No. 4-212888, No. 4-24199
No. 4, No. 4-261895, No. 4-267194,
Dyes exemplified in JP-A-4-97895 and JP-A-8-156399 can be exemplified.

The dye contained in the porous or granular image-forming substance-containing layer is usually 0.5 to 3 in the layer-forming composition.
0% by weight, preferably in the range of 1 to 20% by weight.

The color developer and color former used in the present invention include bisphenol A and leuco dye, a cobalt complex having ammonia or a primary amine as a ligand, an aromatic dialdehyde, and a silver complex. Various known combinations such as a reducing agent capable of reducing the source and a silver source can be appropriately selected and used according to the intended use.

Of these, in order to obtain a black image, it is preferable to use a reducing agent capable of reducing the silver source and a silver source, since the deviation of the density gradation over time is reduced.

As such a silver source, an organic silver salt, an inorganic silver salt or the like can be appropriately selected and used according to the composition of the material. However, an organic silver source which is stable to light is preferable. As the silver source, for example, a silver salt with an aliphatic carboxylic acid (eg, silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, fumaric acid) Silver, silver tartrate,
Silver furonate, silver riloleate, silver butyrate, silver camphorate and the like, silver salts of aromatic carboxylic acids and other compounds containing a carboxyl group (for example, silver benzoate, silver 3,5-dihydrobenzoate, o-methylbenzoate) Silver acid, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,6-dichlorobenzoate, silver acetamidobenzoate, silver p-phenylbenzoate, silver tannate, silver phthalate, silver terephthalate, Silver salicylate, silver phenylacetate, silver pyromellitate, silver salts such as 3-carboxymethyl-4-methyl-thiazoline-2-thione, etc.), silver salts of compounds containing mercapto or thione groups and derivatives thereof, benzothiazole And silver salts of its derivatives.

Among the above-mentioned organic silver sources, silver salts with aliphatic carboxylic acids, or aromatic carboxylic acids and other carboxyl group-containing ones, from the viewpoints of color development density and dispersion stability when a coating solution is prepared. It is preferable to use a silver salt of the compound.

The amount of the silver source to be added is usually 0.5 to 50% by weight, more preferably 1 to 30% by weight of the porous or granular image forming substance-containing layer or the protective layer forming component.
It is preferable to set it in the range.

Further, in the present embodiment, a color tone adjusting agent may be added to adjust the color tone of the formed silver image. Examples of such a color tone adjusting agent include phthalazine, substituted phthalazin-5-one, and the like. Examples thereof include 2,3-dihydro-1,4-phthalazindione and 2-substituted-3-pyrazolin-5-one. Specific examples of these compounds and other color tone adjusting agents are given below. Are described in JP-A-49-22928, JP-A-49-5019 and JP-A-49-5.
No. 020, No. 50-2524, No. 50-67132
And JP-A-50-114217, JP-A-55-4060 and JP-A-55-32015, and the color tone adjusting agent may be either a layer containing a silver source or a protective layer.

When such a color tone adjusting agent is added, it is usually added in an amount of 0.1 to 2 of the components for forming an image forming layer.
It is preferably in the range of 0% by weight, more preferably 0.5 to 10% by weight.

Specific examples of the organic reducing agent described above include amide oximes such as azine,
2'-bis- (hydroxymethyl) propionyl-β-
A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid such as a combination of phenylhydrazide and ascorbic acid, a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine, a combination of azine and a sulfonamide phenol derivative, Bis-β-naphthol derivative, bis-
Combinations of β-naphthol and 1,3-dihydroxybenzene derivatives, 5-pyrazolones, reductones such as dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone, sulfonamide phenols Derivatives, chromans, 1,4-dihydropyridine derivatives, polyhydric phenol derivatives, ascorbic acid derivatives, unsaturated aldehydes and ketones such as benzyl and diacetyl, 3-pyrazolidone and certain indane-1,3-dione, and the like. be able to.

Further, in the image forming material used in the image forming method of the present invention, another layer may be provided, and the back surface of the first support and the second support is provided with a transporting property and a charging property. May have a backing layer for the purpose of prevention, blocking prevention, and the like.
An undercoat layer may be provided on the side of the support on which the stress relaxation layer and the adhesive layer are laminated in order to improve the adhesion to the support. When the undercoat layer is provided, a surface treatment such as a corona treatment may be performed.

Each of the above-mentioned layers can be formed by using a known coating method, and a coating solution can be prepared by dissolving or dispersing each layer forming component in a solvent.

Examples of the solvent include water, alcohols such as ethanol and propanol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as toluene and xylene, ketones such as methyl ethyl ketone and cyclohexanone, ethyl acetate and butyl acetate. Esters, ethers such as dioxolane and dioxane, halogen-based solvents such as chloroform and dichlorobenzene, nitrogen-containing solvents such as dimethylformamide and N-methylpyrrolidone, and sulfur-containing solvents such as dimethylsulfoxide. Can be used.

For dispersion, a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a cobol mill, a tron mill, a sand mill, a sand grinder, a Sqegvar
i Attritor, high-speed impeller disperser, high-speed stone mill, high-speed impact mill, disper, high-speed mixer, homogenizer, ultrasonic disperser, open kneader, continuous kneader and the like can be used.

To apply the coating liquid for forming each layer prepared as described above, an extrusion type extrusion coater, reverse roll coater, gravure roll coater, air doctor coater, blade coater, air knife coater, squeeze coater , Impregnated coater,
Various known coater stations such as a bar coater, a transfer roll coater, a kiss coater, a cast coater, and a spray coater can be appropriately selected and used.

A plurality of first regions formed by the image forming method of the present invention on which a porous or granular image-forming substance is adhered on a support, and a plurality of first areas where the support does not have an image-forming substance. The binary image composed of the second region is formed on the first support 1 by the coating method described above, on the stress-absorbing layer 2, the heat-active image forming layer 3, the porous or granular image forming layer 4, , And a material obtained by sequentially laminating the release layer 5 and the first adhesive layer 6 and a material obtained by laminating the second adhesive layer 7 on the second support 8 by a coating method. You.

As a method for bonding the two materials, the first adhesive layer 6 and the second adhesive layer 7 are opposed to each other, and are heated and pressed using a heat roll or a hot stamp. Can be. As the conditions for the heating and pressurizing treatment, 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 0.5 to 10 kg / cm, and the transport speed is usually 1 to 1000 mm / sec, preferably 5 to 500 mm / sec. When a hot stamp is used, the heating temperature is from room temperature to 180 ° C., preferably 30 to 150 ° C., and the pressure is usually 0.05 to 10 kg / cm ² , preferably 0.1 to 10 kg / cm ² .
5 kg / cm ² to 5 kg / cm ^2.
５０50 seconds, preferably 0.5-20 seconds.

In the image exposure using high-density energy light, the adhesive force between the heat-active image forming layer 3 and the porous or granular image forming layer 4 in the exposed portion is such that the porous or granular image forming layer 4 and the release layer 5 Any light source can be used as long as the light source has a higher adhesive strength than that of the light source. Among them, in order to obtain high resolution, an electromagnetic wave whose energy application area can be narrowed,
In particular, ultraviolet light, visible light, and infrared light having a wavelength of 1 nm to 1 mm are preferable. Examples of the light source to which such light energy can be applied include a laser, a light emitting diode, a xenon flash lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a tungsten lamp, a quartz mercury lamp, a high-pressure mercury lamp, and the like.
The energy applied at this time can be appropriately selected and used by adjusting the exposure distance, time, and intensity according to the type of the image forming material.

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

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

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.
Even from the support side, the adhesive strength between the thermally active image forming layer 3 and the porous or granular image forming layer 4 is smaller than the adhesive strength between the porous or granular image forming layer 4 and the release layer 5 only in the exposed portion. The exposure method may be any one as long as the exposure method increases, but it is preferable to perform exposure from the first support side in terms of energy efficiency.

Further, as described above, the exposed image forming material can be peeled off by a peeling plate, a peeling roll fixing method using a peeling roll, or a manual peeling method in which the peeling sheet and the image forming material are peeled off without being fixed by hand. Various peeling methods can be used as long as they do not affect image formation.
And a plurality of first areas where the porous or granular image-forming substance formed on the second support side adheres to the support, after exposing from the first support side, and peeling off. FIG. 4 is a cross-sectional view when a binary image including a plurality of second regions having no image forming substance is formed.

In the present invention, a plurality of first regions where the porous or granular image-forming substance formed as described above adheres to the support, and a plurality of first areas where the support does not have the image-forming substance. In order to give the density gradation at the boundary between the first area and the second area in the binary image composed of
Further, a protective layer is laminated.

As a method of laminating a protective layer on such a binary image, a coating method of forming a protective layer by coating and drying, or a transfer method of transferring the protective layer by applying pressure or heat and pressure is performed. It can be provided by a method or the like.

Of these, the use of the transfer method is preferred because the damage to the porous or granular image-forming substance-containing layer can be reduced.

In the case where the protective layer is provided by using such a transfer method, a base material having heat sealing properties or a laminate material in which the base material and the adhesive layer are integrated can be used. Laminate materials include heat-resistant acrylic esters, methacrylic esters, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, nylon, aromatic polyamide, and poly. Ethylene-vinyl acetate resin, ethylene-ethyl acrylate resin as an adhesive layer on one side of a transparent or translucent plastic film support such as ether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide resin, etc. Resin, ethylene-acrylic acid resin, ionomer resin, polybutadiene resin, polyamide resin, polyurethane resin, polyvinyl chloride resin, acrylic resin, polystyrene resin, polyester resin, tackifier (for example, phenol resin, rosin resin, terpene resin, The thickness of the plastic film support on which the heat-adhesive resin of petroleum resin is provided is 6 to 100 μm depending on the purpose.
The thickness of the adhesive layer is 5 to 50 μm according to the surface condition of the material to be transferred. The surface of the adhesive layer may be embossed to prevent blocking. Thermal bonding is performed by heat and pressure.

As the laminating material, a known laminating apparatus such as a pressure roll, a stamper, a heat roll, and a hot stamp can be appropriately selected and used depending on the kind of the protective material. The pressure when using a pressure roll is usually 0.1
~ 20 kg / cm is preferable, and more preferably 0.5 ~
10 kg / cm, and the conveying speed is usually 0.1 to 1
000 mm / sec, more preferably 0.5 to 5
The pressure when using a stamper is usually preferably 0.05 to 10 kg / cm ² ,
The pressure is more preferably 0.5 to 5 kg / cm ² , and the pressurization time is usually preferably 0.1 to 50 seconds, more preferably 0.5 to 20 seconds. The heating temperature when using a heat roll is usually preferably from 60 to 200 ° C, more preferably from 80 to 180 ° C, and the pressure is usually 0.1
~ 20 kg / cm is preferable, and more preferably 0.5 ~
10 kg / cm, and the conveying speed is usually 0.1 to 1
000 mm / sec, more preferably 0.5 to 5
The heating temperature when using a hot stamp is usually preferably 60 to 200 ° C, more preferably 80 to 150 ° C, and the pressure is usually 0.05 to 10 kg / cm ^2. Preferably, more preferably 0.5 to 5 kg / cm ² , and the heating time is usually 0.1
-50 seconds is preferable, and 0.5-20 seconds is more preferable.

Further, a transfer foil as shown in FIG. 3 can be used as the protective layer, and the transfer foil shown in FIG.
The release layer 10, the durability layer 11, and the adhesive layer 12 are laminated.

As the transfer foil used in the present invention, a commercially available transfer foil may be used as it is, or Japanese Patent Application Laid-Open Publication No.
No. 04008, 9-502670 and the like may be used.

On the other hand, when a transfer foil containing a protective layer containing a metal ion supply compound, a color developer or a color former, etc., is prepared, a heat-resistant acrylic acid ester, methacrylic acid ester, polyethylene terephthalate, polybutylene terephthalate is used. , Polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, nylon,
A material in which a release layer and an adhesive layer are laminated on one side of a base material such as a resin such as aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, and polyetherimide can be used. A layer in which a durable layer or the like for the purpose of preventing oxygen, improving durability, improving solvent resistance, preventing static electricity, or the like is laminated between the layer and the adhesive layer can also be suitably used.

The thickness of the substrate is usually 3 to 50 μm, preferably 10 to 30 μm.

As the release layer, a high glass transition temperature (Tg)
Resins such as acrylic resins, polyvinyl acetal resins, resins such as polyvinyl butyral resins, waxes, silicone oils, fluorine compounds, polyvinyl pyrrolidone resins having water solubility, polyvinyl alcohol resins, methyl cellulose resins, and hydroxy cellulose resins. And the thickness is preferably 0.1 to 2 μm.

The adhesive layer may be any of those having adhesiveness at normal temperature or those exhibiting adhesiveness by applying heat or pressure. For example, a resin having a low softening point, an adhesive agent, a hot solvent, It can be formed by appropriately selecting a filler or the like.

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

When a dye capable of chelating with a metal ion is used in a plurality of first regions where the porous or granular image-forming substance is adhered on the support, the adhesive layer for forming the protective layer is used. It is preferable to include a metal ion supply compound. Examples of such a metal ion supply compound include salts composed of a metal ion and an inorganic or organic anion, a coordination metal ion complex, and the like. There is one represented by the general formula (1).

Formula (1) [M _l ⁺ (X _m ⁻ ) _o (Y) _p ] (Z _n ) _{q wherein} M is a metal, X is a ligand of an anion, and Y is a neutral ligand. Ligand, Z represents a counter ion, l is a natural number of 1 to 5, m
Is a natural number of 1 to 6, n is -2 to 2 (n ≠ 0), o, p,
q represents an integer of 0 to 6, respectively. Hereinafter, the compound represented by formula (1) will be described in detail.

Examples of the metal ion represented by M _l ⁺ include silver (I), aluminum (III), gold (III), cerium (III, IV), cobalt (II, III), and chromium (II).
I), copper (I, II), europium (III), iron (II, II)
I), gallium (III), germanium (IV), indium (III), lanthanum (III), manganese (II), nickel (II), palladium (II), platinum (II, IV), rhodium (II, III) ), Ruthenium (II, III, IV), scandium (III), silicon (IV), samarium (III), titanium (IV), uranium (IV), zinc (II), zirconium (I
V) and the like. Among these, a bidentate dye is preferably a transition metal ion capable of coordination at a tetradentate or hexadentate, and a tridentate dye is preferably a hexadentate dye. Are preferred. Particularly preferred transition metal ions are zinc (II), nickel (II) and cobalt (I
I, III), copper (II), rhodium (II, III), ruthenium (II, III), palladium (II), and platinum (II, IV).

[0083] Further, X _m ^- In Examples of the anion ligand represented, halide ions, hydroxy ions, nitrate ions, carboxylate ions, cyano ion, peroxy ions, acetylacetonate ions and derivatives thereof, salicylaldehyde phenol Latet ions and derivatives thereof, glycinate ion, thiocyanate ion,
Examples include azide ion, carbonate ion, oxalate ion, sulfate ion, and oxalite ion.

The neutral ligand represented by Y includes ammonia, water, triphenylphosphine, ethylenediamine,
1,3-propanediamine, 2,2'-bipyridine,
1,10-phenanthroline, glycinamide, diethylenetriamine, 2,2 ′, 2 ″ -terpyridine, triethylenetetramine and the like can be mentioned.

[0085] Further, the represented counterion in Z _n, in order to charge neutrality, the anion or cation as needed. Examples of such anions include halide ion, sulfite ion, sulfate ion, alkyl or aryl sulfonate ion, nitrate ion, nitrite ion, perchlorate ion, carboxylate, salicinate, benzoate, hexafluorophosphate, tetrafluoroborate and the like. And examples of the cation include lithium, sodium, potassium, ammonium, and phosphonium.

Further, when a color developing agent is contained in a plurality of first regions where the porous or granular image forming substance is adhered on the support, a color developing agent is contained. A developer is contained in each of the adhesive layers. As the color former and the color developer, those described in the above-mentioned image forming material can be appropriately selected and used in a form suitable for the color development form.

The thickness of the above-mentioned adhesive layer is usually 0.05 to 20.
μm, preferably 0.1 to 10 μm.

The durable layer has an elastic resin layer, a durable resin layer, a photo-curing resin layer, a thermosetting resin layer, etc. for the purpose of cushioning for absorbing unevenness of the image and protecting the transferred image. It can be selected and provided as appropriate according to the application.

Various additives such as a filler, an antistatic agent, a release agent, a tackifier, and a light stabilizer may be added to each layer as long as the object of the present invention is not impaired.

The transfer of the transfer foil to the binary image can be usually performed by means such as a thermal head, a heat roll, a hot stamp, etc., which can apply pressure while heating.

The transfer foil can be transferred under heat roll or hot stamping conditions for laminating the laminating material, and when a thermal head is used, can be transferred under the conditions used for melt transfer or heat diffusion transfer. As a method of peeling the base material, a method of peeling the image forming material after exposure can be appropriately selected and used, and the transfer foil of FIG. 3 is transferred to the image of FIG. 1 shows a cross-sectional view of the image recording medium of the present invention.

In the image forming method of the present invention, a plurality of first regions where a porous or granular image forming substance is adhered on a support, and a plurality of first areas where the support does not have an image forming substance. At the boundary of the binary image composed of the second area, the dye, developer or coloring agent contained in the first area having a high image density is diffused into the protective layer to give a density gradation.
In other words, the diffusivity of the dye, developer or color former into the protective layer determines the density gradient between the first and second regions. Therefore, the dye contained in the first region, the type of the developer or the color former, the material of the layer that adheres to the image forming layer of the protective layer, the metal ion supplying material, the color former that develops color with the developer, and the color former are An image recording body having various gradations can be obtained depending on the type and amount of the color developing agent or the method of pressurizing or heating and pressurizing.

[0093]

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 As a first support, an easy-contact surface of a 38 μm-thick polyethylene terephthalate film [T100E, manufactured by Diafoil Hoechst Co., Ltd.] was mixed with a mixed solvent of toluene / methyl ethyl ketone = 1/1. A solution of a styrene-based resin [manufactured by Mitsui Toatsu Chemicals, Inc., Lightac A 200PC] dissolved at 5% solid content was applied and dried using a bar coater to form an undercoat layer having a dry thickness of 0.5 μm.

Then, toluene / methylene chloride = 4/3
An acrylic resin [Rohm and Haas Japan Co., Ltd., Paraloid B-44] and an infrared absorbing dye [Nippon Kayaku Co., Ltd., Kayasorb IR820B] were added to a mixed solvent of 8
To 100 parts of a 30% solids solution mixed at a ratio of 3.3 / 16.7, a styrene resin [Scripset 540, manufactured by Monsanto Co., Ltd.] and sodium dodecylbenzenesulfonate in a ratio of 75/25 to distilled water. Mixed solids 1
100 parts of a 0% solution was mixed, the organic solvent was removed while ultrasonically dispersing, and then a polyethylene dispersion diluted to a solid content of 10% [Microflat CJ-75S manufactured by Koyo Chemical Co., Ltd.] ] Was added and the mixture was ultrasonically dispersed to prepare a coating solution. The coating solution was applied and dried using a bar coater, and the thermally active image forming layer having a dry thickness of 0.75 μm was formed on the undercoat layer. Formed.

On the thus formed heat-active image forming layer, carbon black having an average particle diameter of 0.08 μm, polyvinyl alcohol [Gohsenol EG-30, manufactured by Nippon Synthetic Chemical Co., Ltd.] and a phosphate ester [Toho Chemical Co., Ltd.] Industrial Co., Ltd.
Manufactured by Phosphanol RE610].
The mixture was dispersed in distilled water at a ratio of 18 using a sand mill at 20% to prepare a dispersion. To 100 parts of this dispersion, 10 parts of a developer dispersion [manufactured by Chukyo Yushi Co., Ltd., Hydrine F-568] diluted with distilled water to a solid content of 20% was added, and then ultrasonically dispersed to obtain a coating liquid. Was prepared.

The coating solution prepared as described above was applied and dried by using an extrusion coater to obtain a dry thickness of 0.75 μm.
m of the porous imaging layer was formed.

Further, a styrene resin [Scripset 540, manufactured by Monsanto Co., Ltd.] and silica [Aerogel 200, manufactured by Nippon Aerogel Co., Ltd.] were dissolved and dispersed in distilled water at a ratio of 9.1 / 90.9. 100 parts of a solution having a solid content of 10% and a polyethylene dispersion diluted with the solution to a solid content of 10% [Microflat C manufactured by Koyo Chemical Co., Ltd.]
J-75S] was added, and the mixture was ultrasonically dispersed to prepare a coating liquid. The coating liquid was applied and dried using an extrusion coater, and a release layer having a dry thickness of 0.5 μm was formed on a porous layer. Formed on the image forming layer.

Separately, a 188 μm polyethylene terephthalate film [Tray Co., Ltd .;
60], methyl ethyl ketone / toluene = 1 /
Polyester resin (manufactured by Goodyear, Vitell PE-200) having a solid content of 20% dissolved in the mixed solvent of No. 1 was applied and dried using an extrusion coater, and the dried thickness was 10 μm.
Was formed.

A heat-pressurizing treatment using a heat roll [roll temperature: 70 ° C., transfer speed: 80 mm / sec., And the release layer surface of the first support and the adhesive layer surface of the second support together]
The pressure was set to 6.0 kg / cm], and the resultant was laminated to produce an image forming material.

As a transfer foil for laminating a protective layer,
As a substrate, a 24 μm polyethylene terephthalate film [T100 manufactured by Diafoil Hoechst Co., Ltd.]
5% acrylic resin dissolved in a mixed solvent of toluene / methyl ethyl ketone = 6/4 [manufactured by Mitsubishi Rayon Co., Ltd.
DIAnal BR88] was applied using a bar coater and dried to form a durable layer having a thickness of 0.8 μm. Next, a vinylidene chloride resin [Saran Resin F-216, manufactured by Asahi Kasei Kogyo Co., Ltd.] diluted to a solid content of 10% dissolved in a mixed solvent of methyl ethyl ketone / toluene = 2/1 was extruded with a coater and dried. A 7 μm durable layer was formed.

Next, 10 parts of polyvinyl alcohol [Gosenol GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.] dissolved in distilled water at a solid content of 10%, and a dispersion of a leuco dye diluted to a solid content of 30% with distilled water [ Chukyo Yushi Co., Ltd., 10 parts of High Micron H-638] and a solid content of 30 with distilled water
% Of a dispersion of m-terphenyl [manufactured by Chukyo Oil & Fats Co., Ltd., High Micron G-991], and redispersed by ultrasonic dispersion to obtain a color former having a solid content of 21.1%. A dispersion was prepared. Add 50 parts of this dispersion with distilled water
100 parts of an ethylene copolymer [Toyo Morton Co., Ltd., Adcoat 37P295] diluted to 1.1% was added,
After ultrasonic dispersion, this coating solution was applied and dried with an extrusion coater to form a 1.5 μm-thick adhesive layer containing a color former, thereby obtaining a transfer foil.

Using the above-described image forming material, the focal point is adjusted to the interface between the thermally active image forming layer and the porous or granular image forming layer, and 256 levels of postscript data (1 × 1 cm) are obtained. Using PS data), screen ruling 250 lines, halftone dot square, screen angle 4
After exposure at 5 ° with an EV laser proofer [manufactured by Konica Corporation, rotation speed: 600 rotations, power: 50%], the film is peeled off and a porous or granular image-forming substance adheres to the support. A binary image consisting of a plurality of first areas and a plurality of second areas where the support did not have an image forming substance was formed.

Next, a protective layer was formed on the image by using a heat roll [heating temperature: 150 ° C., pressure: 20] using the above-mentioned transfer foil.
0 g / cm, speed;] to obtain an image recording body having a protective layer laminated thereon.

The density of 256 gradations of the formed image recording medium was determined by the visual density of a densitometer [X-rite: X-rite
lite 310TR] and the boundary between a plurality of first regions where the porous or granular image forming substance is adhered on the support and a plurality of second regions not having the image forming material. Was measured with a microdensitometer [manufactured by Konica Corporation, Konica microdensitometer PDM-7 type BR]. The measured results are shown in FIGS. In addition, the visual density of the densitometer was indicated by a value obtained by subtracting the value of the density of the entire exposed portion.

Example 2 As a first support, an easy-contact surface of a readily-treated 38 μm polyethylene terephthalate film [T100E, manufactured by Diafoil Hoechst Co., Ltd.] was mixed with a mixed solvent of toluene / methyl ethyl ketone = 1/1. A solution of a styrene-based resin [manufactured by Mitsui Toatsu Chemicals, Inc., Lightac A 200PC] dissolved at 5% solid content was applied and dried using a bar coater to form an undercoat layer having a dry thickness of 0.5 μm.

Then, toluene / methylene chloride = 4/3
86. An acrylic resin [Rohm and Haas Japan Co., Ltd., Paraloid B-44] and an infrared absorbing dye [Nippon Kayaku Co., Ltd., Kayasorb CY-10] in a mixed solvent of 86.
30% solids solution 10 mixed at a ratio of 5 / 13.5
In 0 parts, distilled water was added to sodium diethylhexylsulfosuccinate and polyvinyl alcohol [Nippon Synthetic Chemical Co., Ltd.]
Co., Ltd., Gosenol EG-30] at a ratio of 13.8 / 86.2, mixing 78.4 parts of a 10% solids solution and removing the organic solvent while ultrasonically dispersing to prepare a coating liquid. This coating solution was applied and dried using a bar coater to form a thermally active image forming layer having a dry thickness of 0.5 μm on the undercoat layer.

On the heat-active image forming layer formed as described above, carbon black having an average particle size of 0.08 μm, polyvinyl alcohol [Gohsenol EG-30, manufactured by Nippon Synthetic Chemical Co., Ltd.] and phosphate ester [Toho] Phosphanol RE610 manufactured by Chemical Industry Co., Ltd.]
Dispersion A was prepared at a ratio of 0.18 in distilled water at a solid content of 20% using a sand mill. Separately, 12 parts of silver behenate and 0.04 part of behenic acid were added to 80 parts of polyvinyl alcohol [Gosenol GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.] dissolved in distilled water at a solid content of 10%. To prepare a silver source dispersion B having an average particle diameter of 0.10 μm and a solid content of 21.8%.

After 100 parts of the dispersion A and 18 parts of the dispersion B prepared as described above were mixed and subjected to ultrasonic dispersion, the coating liquid was applied and dried using an extruder coater to obtain a porous material having a dry thickness of 0.75 μm. Was formed.

Further, 10 parts of a solution obtained by dispersing a copolymer of methyl methacrylate and butyl methacrylate [supra] and sodium diethylhexylsulfosuccinate at a ratio of 96/4 in distilled water at 20%, and polyvinyl Alcohol [Gosenol GL manufactured by Nippon Synthetic Chemical Co., Ltd.
-05] and 11 parts of a solution of silica [Aerogel 200, manufactured by Nippon Aerogel Co., Ltd., Aerogel 200] dispersed in distilled water at a ratio of 1/10 at 20%, and applied and dried using an extrusion coater. A release layer having a dry thickness of 0.5 μm was formed on the porous image forming layer.

Separately, a polyethylene terephthalate film of 188 μm as a second support [Tray Co., Ltd .;
60], methyl ethyl ketone and toluene 1: 1
A polyester resin (manufactured by Goodyear, Vitell PE-200) having a solid content of 20% dissolved in a mixed solvent was applied and dried using an extrusion coater to form an adhesive layer having a dry thickness of 10 μm.

The heat-pressurizing treatment using a heat roll [roll temperature: 70 ° C., transport speed: 80 mm / sec., And the release layer surface of the first support and the adhesive layer surface of the second support together]
The pressure was set to 6.0 kg / cm], and the resultant was laminated to produce an image forming material.

Further, as a transfer foil for laminating a protective layer,
An acrylic resin dissolved in a mixed solvent of 20% solids methyl ethyl ketone / toluene = 1/1 [Dianal, manufactured by Mitsubishi Rayon Co., Ltd.] on a 26 μm thick polyethylene terephthalate film [# 26X45 manufactured by Toray Industries, Inc.] BR87 / BR64 = 7/3] 100 parts of a solution is mixed with a silica dispersion having a solid content of 25% [manufactured by Nippon Shokubai Co., Ltd.
An organosilica sol CX-SZ] was mixed in an amount of 20 parts to prepare a coating solution, and the coating solution was applied and dried using a bar coater to form a release layer / durable layer having a dry thickness of 2.0 μm.

Next, 100 parts of an ethylene resin [Evalex EV40Y, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.] dissolved in a mixed solvent of methyl ethyl ketone / toluene = 1/1 in a solid content of 10%, and a solid content of 10% 25 parts of a carnauba dispersion [Microflat CR-4K, manufactured by Koyo Chemical Co., Ltd.] diluted with a mixed solvent of methyl ethyl ketone / toluene = 1/1, and 25 parts of propyl gallate dissolved in methyl ethyl ketone at a solid content of 10%. A coating liquid was prepared by adding the coating liquid, and the coating liquid was applied and dried using an extrusion coater to form a developer-containing adhesive layer having a dry thickness of 2.0 μm to obtain a transfer foil.

Using the above-described image forming material, the focal point is adjusted to the interface between the heat-active image forming layer and the porous or granular image forming layer, and 256 levels of postscript data (1 × 1 cm) are obtained. Using PS data), screen ruling 250 lines, halftone dot square, screen angle 4
5 ゜ Trend setter [Cleo, rotation speed: 60 rotations /
And a plurality of first areas where the porous or granular image-forming substance adheres to the support after being exposed to light, and a plurality of areas where the support does not have the image-forming substance. , A binary image was formed.

Then, a protective layer was formed on the image by using a heat roll [heating temperature: 150 ° C., pressure: 20] using the above-mentioned transfer foil.
0 g / cm, speed;] to form an image recording body having a protective layer laminated thereon.

The density of 256 gradations of the formed image recording medium was measured using the visual density of a densitometer [X-rite: X-rite.
lite 310TR] and the boundary between a plurality of first regions where the porous or granular image forming substance is adhered on the support and a plurality of second regions not having the image forming material. Was measured with a microdensitometer [manufactured by Konica Corporation, Konica microdensitometer PDM-7 type BR]. The measured results are shown in FIGS.

Example 3 As a first support, a polyurethane [diluted to 20% with distilled water] was applied to an easy-contact surface of a readily-treated 38 μm polyethylene terephthalate film [T100E, manufactured by Diafoil Hoechst Co., Ltd.] ICI Japan Co., Ltd.
Neotack R-9819] was applied and dried using a bar coater to form a stress absorbing layer having a dry thickness of 0.5 μm.

Next, toluene / methyl ethyl ketone =
Styrene resin dissolved in 1/1 mixed solvent at 5% solid content [Mitsui Toatsu Chemical Co., Ltd., Lightac A 200P
C] The solution was applied and dried using an extrusion coater to form a thermally active image forming layer having a dry thickness of 0.9 μm on the stress absorbing layer.

A carbon black having an average particle diameter of 0.08 μm, polyvinyl alcohol [Gohsenol EG-30, manufactured by Nippon Synthetic Chemical Co., Ltd.], a styrene-based dispersant [Johnson] Wax Co., Joncryl 67], 1,4-butanediol diglycidyl ether is dispersed in distilled water at a ratio of 5/1 / 0.5 / 0.18 at 20% using a sand mill to prepare dispersion A. did. Separately, 4 parts of propyl gallate and 1 part of a surfactant [Triton X200 manufactured by Rohm and Haas Japan KK] were mixed with 20 parts of distilled water, and then dispersed using a sand mill to obtain an average particle diameter of 0.05 μm. A dispersion B of a developer having a solid content of 20% was prepared.

Dispersion A100 prepared as described above
Was mixed with 10 parts of Dispersion B and subjected to ultrasonic dispersion. The coating liquid was applied and dried using an extrusion coater to form a porous image forming layer having a dry thickness of 1.0 μm.

On this porous image forming layer, polyvinyl alcohol [Gosenol GL-, manufactured by Nippon Synthetic Chemical Co., Ltd.]
05], a maleic anhydride copolymer resin (GAF, Gantrez S-97), a fluorine-based surfactant [Sumitomo 3M Co., Ltd., Florad FC-120] on 21/0.
To 100 parts of a solution of 6 / 0.2 dissolved in distilled water at 15%, 20.6 parts of silica [Aerogel 200, manufactured by Nippon Aerogel Co., Ltd.] was added and ultrasonically dispersed, and further 20% with distilled water. 6.88 parts of a styrene-based resin [John Krill 87, manufactured by Johnson Wax Co.] diluted in water was added, and the mixture was ultrasonically dispersed to prepare a coating solution. The coating solution was extruded using an coater and dried. A release layer having a dry thickness of 1.0 μm was formed.

Further, on the release layer, vinylidene chloride (Dalane SL-11, manufactured by WR Grace Co., Ltd.) having a solid content of 20% diluted with distilled water and an ester of sodium sulfosuccinate [Aerosol, manufactured by Air Products & Chemicals Co., Ltd.] [OT] was applied and dried using an extrusion coater to form a first adhesive layer having a dry thickness of 2.5 μm.

Separately, a 188 μm polyethylene terephthalate film [Tray Co., Ltd .;
60], an acrylic resin [Elvasite 2045, manufactured by EI DuPont Nemours, Inc.] and a 50% acrylic resin [Dresco RAC-10, manufactured by Dock Resin Co., Ltd.]
2], methoxyhydroquinone, 2,2-dimethoxy-
2-phenylacetophenone [Nihon Ciba Geigy Co., Ltd.
, Irgacure 651], antioxidant [1: 1 blend of Irganox 1010 / Irganox 1035, manufactured by Ciba-Geigy Japan Ltd.], trimethylolpropane triacrylate [Kayarad TMPTA, manufactured by Nippon Kayaku Co., Ltd.] ], Ethyl acrylate 11/240
/0.1/14/0.7/50/13 dissolved in methyl ethyl ketone so as to have a solid content of 30%, applied and dried using an extrusion coater, and dried to a second thickness of 17 μm.
An adhesive layer was formed.

The first adhesive layer surface of the first support prepared as described above and the second adhesive layer surface on the second support were combined and heated and pressed using a heat roll [roll temperature]. 40 ° C., conveying speed; 100 mm / sec, pressure 6.0 k
g / cm], and then irradiate ultraviolet rays from the second support side to bond the first adhesive layer surface of the first support and the second adhesive layer surface on the second support to bond the image forming material. Produced.

As a transfer foil for laminating a protective layer,
On a 24 μm-thick polyethylene terephthalate film [T100 manufactured by Diafoil Hoechst Co., Ltd.], 1
5 parts of an ethylene-vinyl acetate copolymer [manufactured by DuPont-Mitsui Polychemicals Co., Ltd., Everex EV210] dissolved in a mixed solvent of toluene / cyclohexanone = 9/2 to a solid content of 5%, 15% wax dispersion [Microflat CE-15 manufactured by Koyo Chemical Co., Ltd.]
5] was mixed with 95 parts to prepare a coating solution, which was coated on the substrate with a bar coater and dried to form a release layer having a dry film thickness of 1.0 μm. Then, as a durable layer, dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd. DPHA], isocyanuric acid EO-modified triacrylate [Toa Gosei Chemical Industry Co., Ltd.]
Manufactured by Aronix M-315], 4-methoxyphenol, 2,2-dimethoxy-2-phenylacetophenone [Irgacure 651 manufactured by Nippon Ciba Geigy Co., Ltd.],
Tetrakis [methylene (3,5-di-tert-butyl-4
-Hydroxyhydrocinnamate)] methane [Irganox 1010, manufactured by Nippon Ciba Geigy Co., Ltd.], thiodiethylenebis {(3,5-di-tert-butyl-4-hydroxy) hydrocinnamate} methane [Nippon Ciba Geigy ( Manufactured by Irganox 1035].
After adding and dissolving 0.025 / 4.043 / 0.131 / 0.131 parts to prepare a coating solution, coating and drying using an extrusion coater, and then irradiating with ultraviolet rays, the coating solution having a thickness of 1.5 μm was obtained. A durable layer was formed.

Next, 12 parts of silver behenate and 0.04 part of behenic acid were added to 80 parts of polyvinyl alcohol [Gosenol GL-05, manufactured by Nippon Synthetic Chemical Co., Ltd.] dissolved in distilled water at a solid content of 10%. The mixture was dispersed using a sand mill to prepare a silver source dispersion having an average particle size of 0.10 μm and a solid content of 21.8%.
Hydroxypropylcellulose dispersed and dissolved in distilled water so that the solid content ratio becomes 1/9 at 8% [Nippon Soda Co., Ltd.
10 made of HPC-L] and an acrylic resin [Arontack HVC-5200 manufactured by Toa Gosei Chemical Industry Co., Ltd.]
0 parts were added, and after ultrasonic dispersion, this coating solution was applied and dried by an extrusion coater to form an adhesive layer containing a silver source having a thickness of 1.0 μm to obtain a transfer foil.

Using the above-mentioned image forming material and the transfer foil, the focal point is set to the interface between the heat-active image forming layer and the porous or granular image forming layer, and the gradation of 256 gradations where one gradation is about 1 × 1 cm is obtained. Using data (RAW data), exposure and peeling were performed with a dry imager 1417D (manufactured by Konica Corporation), and then an image recording body was formed by laminating a protective layer on the image.

The density of 256 gradations of the formed image recording medium was determined by the visual density of a densitometer [X-rite: X-rite.
lite 310TR] and the boundary between a plurality of first regions where the porous or granular image forming substance is adhered on the support and a plurality of second regions not having the image forming material. Was measured with a microdensitometer [manufactured by Konica Corporation, Konica microdensitometer PDM-7 type BR]. The measured results are shown in FIGS.

Example 4 As a first support, an easily contacted surface of a 24 μm polyethylene terephthalate film [T100E, manufactured by Diafoil Hoechst Co., Ltd.] was diluted with distilled water to a solid content of 20%. Polyurethane [NEOC T-9619 / NEORET R-9, manufactured by ICI Japan Co., Ltd.
637 = 90/10] using a bar coater and drying to form a stress absorbing layer having a dry thickness of 2.4 μm.

Next, toluene / methyl ethyl ketone =
Styrene resin dissolved in 1/1 mixed solvent at a solid content of 20% [Lightac A 200P, manufactured by Mitsui Toatsu Chemicals, Inc.]
C] The solution was applied and dried using an extrusion coater to form a thermally active image forming layer having a dry thickness of 1.3 μm.

On the heat-active image forming layer formed as described above, carbon black and polyvinyl alcohol having an average particle diameter of 0.08 μm [manufactured by Nippon Synthetic Chemical Co., Ltd .; Gohsenol EG-3
0], 1,4-butanediol diglycidyl ether,
5 / 1.5 / 0.18 of a fluorinated surfactant [Fluorad FC-171, manufactured by Sumitomo 3M Limited]
The composition mixed at a weight ratio of /0.005 was dispersed using a sand mill to prepare a dispersion A.

Separately, 1/1/1 of Dye 1, Dye 2 and Dye 3
1.5 parts of a surfactant [Triton X200, manufactured by Rohm and Haas Japan KK] was mixed with 1.5 parts of distilled water 3
After mixing with 0 parts, the mixture was dispersed using a sand mill to prepare a dispersion B of a metal ion having an average particle diameter of 0.15 μm and a dye capable of chelating with a metal ion having a solid content of 14.3%.

After 100 parts of the dispersion A and 28 parts of the dispersion B prepared as described above were mixed and ultrasonically dispersed, the coating liquid was applied and dried using an extruder coater to obtain a dry thickness of 1.0 part.
A μm porous imaging layer was formed.

On the porous image-forming layer formed as described above, polytetrafluoroethylene particles having an average particle diameter of 0.2 μm, and silica [Nippon Aerogel Co., Ltd.] were added to distilled water so as to have a solid content of 10%. Manufactured by Aerogel 200],
Hydroxyethyl cellulose [Daicel Chemical Industries, Ltd.]
Manufactured by HEC Daicel SP250]
The composition mixed at a weight ratio of 1 / 0.1 was dispersed using a sand mill, and this solution was applied and dried using an extrusion coater to form a release layer having a dry thickness of 1.0 μm.

Further, an acrylic resin solution having a solid content of 40% [NEOCRYL BT52, manufactured by ICI Japan Ltd.]
0] was applied and dried using an extrusion coater, and a first adhesive layer was formed on the release layer to a dry thickness of 2.2 μm.

Separately, a 188 μm polyethylene terephthalate film [produced by Toray Industries, Inc .;
60], methyl ethyl ketone and toluene 1: 1
Acrylic resin [Dianal BR112, manufactured by Mitsubishi Rayon Co., Ltd.], trimethylolpropane triacrylate [Kayarad TMPTA, manufactured by Nippon Kayaku Co., Ltd.], 4-methoxyphenol, 2,2-
Dimethoxy-2-phenylacetophenone [Nippon Ciba-Geigy Co., Ltd., Irgacure 651], tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane [Nippon Ciba-Geigy Co., Ltd .; Irganox 1010], thiodiethylenebis {(3,5-di-tert-butyl-4-hydroxy)
Hydrocinnamate @ methane [Nihon Ciba Geigy Co., Ltd.
Manufactured by Irganox 1035], 11.90 / 2.82
A composition having a solid content of 30% mixed at a weight ratio of /0.007/1.14/0.037/0.037 parts was applied and dried using an extruder coater, and dried with a UV-curable 10 μm thick. Two adhesive layers were formed.

The first adhesive layer surface of the first support and the second adhesive layer surface on the second support were combined and heated and pressed using a heat roll [roll temperature; 40 ° C., transport speed; 10
0 mm / sec, pressure 6.0 kg / cm], and then irradiate ultraviolet rays from the second support side to cause a gap between the first adhesive layer surface of the first support and the second adhesive layer surface on the second support. By pasting, an image forming material was prepared.

As a transfer foil for laminating a protective layer,
Polyethylene dispersion [Koyo Chemical Co., Ltd.] diluted to a solid content of 10% with distilled water on a 26 μm-thick polyethylene terephthalate film [# 26X45 manufactured by Toray Industries, Inc.]
Manufactured by Microflat CJ-75S] and a polyester dispersion diluted to 10% solids with distilled water [Toyobo Co., Ltd.
Co., Ltd., Dianal MD1200] was mixed at 9/1 to prepare a coating solution, and the coating solution was applied and dried using a bar coater to form a release layer having a dry thickness of 5.0 μm. Then, at a solid content of 10%, methyl ethyl ketone / toluene = 1
/ 100 parts of polyvinyl butyral [Sekisui Chemical Co., Ltd., Eslek BX55] dissolved in a mixed solvent of 1/1 and 4 parts of an isocyanate compound having a solid content of 50% [Nippon Polyurethane Industry Co., Ltd., Coronate 3041] are mixed. Then, after coating and drying using an extrusion coater, 48 ° C. at 50 ° C.
After heat curing for a time, a durable layer having a thickness of 1.0 μm was formed.

Then, polyvinyl butyral diluted with a mixed solvent of methyl ethyl ketone / toluene = 1/1 at a solid content of 10% [Eslec BL-, manufactured by Sekisui Chemical Co., Ltd.]
1] 1 dissolved in 100 parts of solution with methyl ethyl ketone
80 parts of a solution containing 0% of a metal ion supply compound is added, and this coating solution is applied and dried using an extruder to form a 1.5 μm-thick metal ion supply compound-containing adhesive layer. Obtained.

[0141]

Embedded image

Using the above-described image forming material and transfer foil, the focal point is adjusted to the interface between the heat-active image forming layer and the porous or granular image forming layer, and a 256-tone post in which one tone is about 1 × 1 cm. Using script data (PS data), an image with a resolution of 2540 dpi, a screen ruling of 120 l / cm, a halftone dot square, and a screen angle of 45 ° using a dry setter (manufactured by Heidelberg Prepress Co., Ltd., light value: 100) Exposure, peeling, and then, an image recording body in which a protective layer was laminated on the image was produced.

The density of 256 gradations of the formed image recording medium was measured using the visual density of a densitometer [X-rite: X-rite.
lite 310TR] and the boundary between a plurality of first regions where the porous or granular image forming substance is adhered on the support and a plurality of second regions not having the image forming material. Was measured with a microdensitometer [manufactured by Konica Corporation, Konica microdensitometer PDM-7 type BR]. The measured results are shown in FIGS.

Comparative Example As a first support, an easy-contact surface of a 38 μm polyethylene terephthalate film [T100E, manufactured by Diafoil Hoechst Co., Ltd.] was treated with a mixed solvent of toluene / methyl ethyl ketone = 1/1. A solution of a styrene-based resin [Light Tack A 200PC, manufactured by Mitsui Toatsu Chemicals, Inc.] dissolved at a solid content of 5% was applied and dried using a bar coater to form an undercoat layer having a dry thickness of 0.5 μm.

Then, toluene / methylene chloride = 4/3
86. An acrylic resin [Rohm and Haas Japan Co., Ltd., Paraloid B-44] and an infrared absorbing dye [Nippon Kayaku Co., Ltd., Kayasorb CY-10] in a mixed solvent of 86.
30% solids solution 10 mixed at a ratio of 5 / 13.5
In 0 parts, distilled water was added to sodium diethylhexylsulfosuccinate and polyvinyl alcohol [Nippon Synthetic Chemical Co., Ltd.]
And Gosenol EG-30] at a ratio of 13.8 / 86.2, and mixing 78.4 parts of a 10% solids solution. The coating solution was prepared, and the coating solution was applied and dried using a bar coater to form a thermally active image forming layer having a dry thickness of 0.5 μm on the undercoat layer.

On the heat-active image forming layer formed as described above, carbon black having an average particle size of 0.08 μm, polyvinyl alcohol [Gohsenol EG-30, manufactured by Nippon Synthetic Chemical Co., Ltd.] and phosphate ester [Toho] Phosphanol RE610 manufactured by Chemical Industry Co., Ltd.]
A solution dispersed in distilled water at a ratio of 0.18 at 20% using a sand mill was applied and dried using an extrusion coater to form a porous image forming layer having a dry thickness of 0.75 μm.

Further, 10 parts of a solution obtained by dispersing a copolymer of methyl methacrylate and butyl methacrylate [supra] and sodium diethylhexylsulfosuccinate at a ratio of 96/4 in distilled water at 20%, and Alcohol [Gosenol GL manufactured by Nippon Synthetic Chemical Co., Ltd.
-05] and 11 parts of a solution of silica [Aerogel 200, manufactured by Nippon Aerogel Co., Ltd., Aerogel 200] dispersed in distilled water at a ratio of 1/10 at 20%, and applied and dried using an extrusion coater. A release layer having a dry thickness of 0.5 μm was formed on the porous image forming layer.

Separately, a 188 μm polyethylene terephthalate film [Tray Co., Ltd .;
60], methyl ethyl ketone and toluene 1: 1
A polyester resin (manufactured by Goodyear, Vitell PE-200) having a solid content of 20% dissolved in a mixed solvent was applied and dried using an extrusion coater to form an adhesive layer having a dry thickness of 10 μm.

The heat-pressurizing treatment using a heat roll [roll temperature: 70 ° C., transport speed: 80 mm / sec., Combined with the release layer surface of the first support and the adhesive layer surface on the second support]
The pressure was set to 6.0 kg / cm], and the resultant was laminated to produce an image forming material.

As a transfer foil for laminating a protective layer,
An acrylic resin dissolved in a mixed solvent of 20% solids methyl ethyl ketone / toluene = 1/1 [Dianal, manufactured by Mitsubishi Rayon Co., Ltd.] on a 26 μm thick polyethylene terephthalate film [# 26X45 manufactured by Toray Industries, Inc.] BR87 / BR64 = 7/3] 100 parts of a solution is mixed with a silica dispersion having a solid content of 25% [manufactured by Nippon Shokubai Co., Ltd.
An organosilica sol CX-SZ] was mixed in an amount of 20 parts to prepare a coating solution, and the coating solution was applied and dried using a bar coater to form a release layer / durable layer having a dry thickness of 2.0 μm.

Next, a solution of an ethylene resin [Evalex EV40Y, manufactured by Du Pont-Mitsui Polychemicals Ltd.] dissolved in a mixed solvent of methyl ethyl ketone / toluene = 1/1 in a solid content of 10% was extruded using a coater and dried. Then, a transfer foil was obtained by forming an adhesive layer having a dry thickness of 2.0 μm.

Using the above-described image forming material, the focal point is adjusted to the interface between the thermally active image forming layer and the porous or granular image forming layer, and 256 levels of postscript data (1 × 1 cm) are obtained. Using PS data), screen ruling 250 lines, halftone dot square, screen angle 4
5 ゜ Trend setter [Cleo, rotation speed: 60 rotations /
And a plurality of first areas where the porous or granular image-forming substance adheres to the support after being exposed to light, and a plurality of areas where the support does not have the image-forming substance. , A binary image was formed.

Next, a protective layer was formed on the image by using the above-described transfer foil on a heat roll [heating temperature: 150 ° C., pressure: 20 ° C.].
0 g / cm, speed;] to form an image recording body having a protective layer laminated thereon.

The density of 256 gradations of the formed image recording medium is determined by the visual density of a densitometer [X-rite: X-rite.
lite 310TR] and the boundary between a plurality of first regions where the porous or granular image forming substance is adhered on the support and a plurality of second regions not having the image forming material. Was measured with a microdensitometer [manufactured by Konica Corporation, Konica microdensitometer PDM-7 type BR]. The measured results are shown in FIGS.

It should be noted that an image having no density gradient at the boundary of the comparative example can be visually discriminated between an exposed portion and an unexposed portion.
While the gradation is also seen stepwise, it is difficult to visually discriminate between the exposed part and the unexposed part in any of the image recording bodies formed in the examples, and the gradation also looks smooth. It was possible to form an image recording body having gradation without reducing the laser spot diameter.

[0156]

According to the present invention, an image forming method for giving an image having binary image densities a density gradation and an image recording medium having a density gradation formed by the method are obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an image forming material used in the image forming method of the present invention.

FIG. 2 is a cross-sectional view when a binary image of the present invention is formed.

FIG. 3 is a sectional view of a transfer foil used as a protective layer of the present invention.

FIG. 4 is a cross-sectional view of the image recording body of the present invention.

FIG. 5 is a graph of transmission density with respect to the number of gradations.

FIG. 6 is a graph of transmission density versus distance in a second region from a boundary of the first region.

[Description of Signs] 1 First support 2 Stress absorbing layer 3 Thermally active image forming layer 4 Porous or granular image forming layer 5 Release layer 6 First adhesive layer 7 Second adhesive layer 8 Second support Body 9 Base material 10 Release layer 11 Durable layer 12 Adhesive layer

Claims (9)

[Claims] 1. A method according to claim 1, wherein the first support has at least one heat-active image-forming layer and contains at least one porous or granular image-forming substance adjacent to the heat-active image-forming layer. An image forming material having at least one adhesive layer and a second support on these layers is exposed to light through a support, and the heat-active image forming layer in the exposed portion is exposed to light. After enhancing the adhesion between the image forming layers, the first area having the image forming substance and the second area not having the image forming substance are peeled between the thermoactive image forming layer and the image forming layer. Is separated into an image material having an adhesive layer and a second support, and then a protective layer is laminated on the image material, whereby a concentration layer is formed at the boundary between the first region and the second region. An image forming method characterized by giving a tone. 2. The image forming method according to claim 1, wherein the method of laminating the protective layer on the image material after separating into the image material includes transferring and laminating the protective layer by applying heat and / or pressure. Method. 3. The image forming method according to claim 1, wherein the exposure is exposure with high-density energy light. 4. The method according to claim 1, wherein the first area having the image forming substance contains a dye.
Item. 5. The dye according to claim 4, wherein the dye is a metal ion.
5. The image forming method according to claim 4, wherein the protective layer contains a metal ion-supplying compound, which is a dye capable of chelating at or above the position. 6. The image forming apparatus according to claim 1, wherein the first region having the image forming substance contains a color developer, and the protective layer contains a color former. Method. 7. The image forming apparatus according to claim 1, wherein the first region having the image forming substance contains a color forming agent, and the protective layer contains a color developing agent. Method. 8. The image according to claim 6, wherein the color former according to claim 7 is a silver source, and the developer is a reducing agent capable of reducing the silver source into a silver image. Forming method. 9. An image recording medium, wherein an image having a density gradation is formed at a boundary between a first area and a second area by the image forming method according to claim 1.