JP2001096914A - Abration image-forming material and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the manufacturing method of an image-forming material and an abrasion image-forming material of a high image durability and a high picture quality, of which the purposes are the stabilization of a protective layer coating property, the extension of the application range of a binder resin and a crosslinking agent to be used, the reduction of the manufacturing period of time and the reduction of the cost. SOLUTION: This ablation image-forming material has a coloring matter layer containing a water-soluble or water-dispersing binder resin and a coloring matter, and a protective layer containing an organic solvent-soluble binder resin, on a supporting body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ablation image forming material capable of obtaining a high-quality image excellent in image durability and production stability, and a method for manufacturing the ablation image forming material.

[0002]

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

For example, JP-A-8-334894, JP-A-8-334894
No.-337053, No.8-337056, No.9-15
No. 849 describes a method and an image-forming material for forming a high-density, high-resolution image with a low residual ratio of an image forming layer by ablation using a high-intensity laser beam.

It is a known fact that in these image forming materials, it is effective to crosslink a binder resin in a color material layer or a protective layer with a crosslinker in order to improve image durability. However, the binder resin and the cross-linking agent, which can be cross-linked by the cross-linking agent, have different solubility in water and organic solvents, respectively, and when they are present in the same coating liquid, coagulation and precipitation may occur in the coating liquid. It is difficult to always ensure the stability of the liquid, and the combination of the binder resin and the crosslinking agent that can be crosslinked by the crosslinking agent is necessarily limited.

Further, the present inventors have found that by providing a protective layer on an ablation image forming material, the image durability after image formation is improved. In order to prevent the protective layer coating solution from penetrating into the color material layer or dissolving the color material layer, a crosslinking agent (curing agent) is added to the color material layer coating solution in advance, and after the color material layer is applied, the protective layer is coated. Since heat treatment must be performed before coating, the time and cost required for production have been high.

In Japanese Patent Publication No. 7-25202, the stability of coating is improved by limiting the solvent used in the coating liquid for the protective layer to a specific type, but sufficient image durability has not been obtained. .

[0007]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. That is, an object of the present invention is to form an image with high image durability and high image quality for the purpose of stabilizing the coating property of the protective layer, expanding the application range of the binder resin and the crosslinking agent to be used, shortening the production time, and reducing the cost. material,
And a method for producing an ablation image forming material.

[0008]

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

An ablation image forming material having a color material layer containing a water-soluble or water-dispersible binder resin and a color material on a support, and a protective layer containing an organic solvent-soluble binder resin, wherein the color material layer is A polyvinyl alcohol resin or a polyvinyl acetal resin as a water-soluble binder resin, and carbon black or graphite as a coloring material, a binder resin crosslinkable by a crosslinking agent on a support, a coloring material layer having a coloring material, and a binder resin. An ablation image forming material having a protective layer having a cross-linking agent for cross-linking the binder resin in the color material layer, being a liquid at a temperature at which the cross-linking agent of the protective layer is heat-treated, a binder resin on a support, a color material And a coloring material layer having a crosslinking agent, and a protective layer having a binder resin capable of being crosslinked by the crosslinking agent Having an ablation image forming material in which the cross-linking agent of the color material layer is capable of cross-linking the binder resin of the protective layer, being a liquid at a temperature at which the cross-linking agent of the color material layer is heat-treated, The transfer-receiving sheet exhibiting adhesiveness faces the protective layer side and is adhered releasably by heat or pressure, and at least one layer selected from the colorant layer and the protective layer contains fine particles different from the colorant, A coating material for a colorant layer having a binder resin crosslinkable by a crosslinking agent, a crosslinking agent and a colorant on a support, and a coating solution for a protective layer having a binder resin and a crosslinking agent crosslinkable by a crosslinking agent are supported in this order. A method for producing an ablation image forming material in which a coating material is dried on a body and then heat-treated to simultaneously crosslink the colorant layer and the protective layer; a binder resin crosslinkable on a support by a crosslinking agent; After providing a color material layer having a color material, a binder resin thereon, a cross-linking agent of the protective layer is transferred into the color material layer by heating the image forming material in which a protective layer having a cross-linking agent is laminated, Method for producing ablation image forming material for crosslinking binder resin of color material layer, After providing a color material layer having a binder resin, a color material, and a crosslinking agent on a support, a binder resin capable of crosslinking with a crosslinking agent thereon A method for producing an ablation image forming material in which a cross-linking agent of a color material layer is transferred into a protective layer by heat-treating an image forming material having a protective layer laminated thereon, and a binder resin of the protective layer is cross-linked.

Hereinafter, the present invention will be described in detail.

The support used in the image forming material of the present invention includes, for example, 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. .

The above-mentioned support is preferably stretched into a film and heat-set in view of dimensional stability. Further, a support having a high transmittance with respect to an image exposure wavelength of laser light is preferable. % Or more, even 70
% Support is preferred. In addition, from the viewpoint of transportability and scratch resistance during the production of the image forming material, a filler such as titanium oxide, zinc oxide, barium sulfate, calcium carbonate, a coloring agent such as a bluing agent, and an antistatic agent as long as the effects of the present invention are not impaired. Etc. may be added.

The thickness of the support is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

The color material layer of the image forming material of the present invention contains at least a color material capable of absorbing laser light and a binder resin.

The coloring material used in the present invention is capable of absorbing the wavelength light of the exposure light source. For example, carbon black, graphite, etc. are preferably used since they are coloring materials having a wide absorption from the ultraviolet region to the visible and infrared regions. it can. In addition, inorganic or organic pigments and dyes are used, and are composed of a single-color, two-color mixed, or three-color mixed pigment-based compound.

Examples of the inorganic pigment include titanium dioxide, carbon black, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium, and calcium. As organic pigments,
Examples include azo-based, thioindigo-based, anthraquinone-based, anthranthrone-based, triphenedioxazine-based pigments, vat dye pigments, phthalocyanine pigments (copper phthalocyanine and derivatives thereof), and quinacridone pigments.
Examples of the organic dye include an acid dye, a direct dye, and a disperse dye.

When the wavelength of the exposure light source is a near infrared ray, examples of the near infrared light absorber include organic compounds such as cyanine, polymethine, azurenium, squarium, thiopyrylium, naphthoquinone, and anthraquinone dyes, and phthalocyanine dyes. , Azo- and thioamide-based organometallic complexes are preferably used.
No. 91, 64-33547, JP-A-1-16068
No. 3, No. 1-280750, No. 1-293342,
2-2074, 3-26593, 3-309
Nos. 91, 3-34891, 3-36093, 3-36094, 3-36095, 3-422
Compounds described in Nos. 81, 3-97589 and 3-103476 are exemplified.

Of these, carbon black and graphite are preferred from the viewpoint of obtaining a high-resolution image with high density.

The content of the coloring material contained in the coloring material layer is preferably about 10 to 99% by weight, more preferably 30 to 95% by weight of the coloring material layer forming components.

Any binder resin can be used without particular limitation as long as it can hold the above-mentioned coloring material. Examples of such a binder resin include polyurethane, polyester, vinyl chloride / vinyl ether copolymer, vinyl chloride / glycidyl. Vinyl chloride resins such as vinyl ether copolymers, vinyl chloride / vinyl acetate copolymers, polyolefin resins such as butadiene / acrylonitrile copolymer, polyvinyl acetal resins such as polyvinyl butyral, cellulose resins such as nitrocellulose, and styrene・ Styrene resin such as butadiene copolymer, acrylic resin such as polymethyl methacrylate, polyamide,
Phenol resins, epoxy resins, phenoxy resins and the like are listed. These resins are dissolved in an organic solvent or water or used as an emulsion in which fine resin particles are dispersed in water.

As the water-soluble binder, gelatin, polyvinyl acetal resin, polyvinyl alcohol resin,
Cellulose resins such as polyvinylpyrrolidone resin, water-soluble nylon and methylcellulose resin are preferred.

As the water-dispersible binder, polyurethane, polyester, polyolefin resins such as butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, and acrylic resin are preferably used.

Examples of the organic solvent-soluble resin include polyvinyl acetal resins such as polyurethane, polyester and polyvinyl butyral; cellulose resins such as nitrocellulose; styrene resins such as styrene / butadiene copolymer; and acrylic resins such as polymethyl methacrylate. resin,
Polyamide, phenol resin, epoxy resin, phenoxy resin and the like are preferably used.

In the present invention, in order to increase the scratching strength of the color material layer during transportation or image formation to be described later,
It is preferable to crosslink the binder resin by thermal crosslinking, active energy crosslinking, moisture crosslinking, or the like using a crosslinking agent. In order to sufficiently perform crosslinking, the coloring material layer is crosslinked by thermal crosslinking and / or active energy ray crosslinking. It is preferred that

The thermally crosslinkable binder resin used for thermal crosslinking and the crosslinking agent added as necessary include a binder resin having a hydroxyl group, a carboxylic acid group or a sulfonic acid group, a crosslinking agent having an isocyanate group, and an epoxy group. Binder resin or crosslinking agent, and a binder resin or a crosslinking agent containing an amino group-containing binder resin or a crosslinking agent or an acid anhydride. Further, a resin that can be thermally cross-linked by using a catalyst or the like is also appropriately selected. Can be used. The crosslinking agent or catalyst is preferably used in an amount of usually 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, based on 100 parts by weight of the thermally crosslinkable binder resin. Is preferred.

In the active energy ray crosslinking, a combination of a conventionally known compound having an ethylenically unsaturated double bond or a compound having an epoxy group with a polymerization initiator or a crosslinking agent can be used.

Specific examples of the compound having an ethylenically unsaturated double bond include compounds described in “11290 Chemical Products”, Kagaku Kogyo Nippo, pages 286 to 294, and “UV · E”.
B Curing Handbook (Raw Materials Edition) "Polymer Publishing Association, 11-
Examples of the compounds described on page 65 include benzoin-based compounds, carbonyl compounds, azo compounds, sulfur compounds, halides, peroxides, and various metal complexes. Examples of the compound having an epoxy group in the molecule include compounds described in “Chemical Products of 11290”, Kagaku Kogyo Nippo, pages 778 to 787, and examples of the polymerization initiator or crosslinking agent include amine compounds and acid compounds. An anhydride, a proton acid generator and the like can be mentioned. The polymerization initiator or the crosslinking agent is usually added and mixed in a range of 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the polymerizable compound. Can be.

Examples of the water-soluble and water-dispersible crosslinking agents include melamine resins, isocyanate compounds, isoxazoles, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds and the like. it can.

For example, in the case of a colorant layer composition containing a cross-linking agent such as polyisocyanate, a treatment for developing a reactive group such as a hydroxyl group or a carboxyl group on the support surface by reacting with the polyisocyanate. By performing the above, the bonding force can be increased. In the case of an image forming composition containing a binder resin having a polar group, the polar group can be expressed on the surface of the support by performing the treatment, and the bonding force can be increased by hydrogen bonding, affinity, or the like.

Among the above-mentioned treatments, for example, the corona discharge treatment is preferably used as the treatment of the present invention because the treatment time is short, the long treatment is easy, and the bonding force after the treatment is relatively stable. Specifically, high frequency and high voltage are applied between the insulated electrode and the grounded conductive roll, and the air is broken down and ionized to generate corona discharge. By passing through the support, the support can be subjected to corona discharge treatment. In addition, as a corona treatment device, there are three types of a spark gap system, a vacuum tube system, and a solid state system depending on the difference in the oscillation system.
The oscillation method is roughly classified into two types, and an appropriate oscillation method can be selected and used according to the application.

The amount of the binder resin is preferably about 1 to 99% by weight, more preferably 5 to 7% by weight of the coloring material layer forming component.
0% by weight.

In the coloring material layer, in addition to the above-mentioned components, a light-to-heat conversion material, a lubricant, a durability improver, a dispersant, an antistatic agent, a filler, a filler, as long as the effects of the present invention are not impaired. And the like.

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 fatty acids having 12 to 18 carbon atoms, such as lauric acid and stearic acid, and amides, alkali metal salts, and alkaline earth metal salts thereof; polyalkylene oxide alkyl phosphates, lecithin, Alkyl polyolefin oxy quaternary ammonium salts; azo compounds having a carboxyl group and a sulfone group; and the like; examples of antistatic agents include cationic surfactants, anionic surfactants, and nonionic surfactants. , Polymeric antistatic agents, conductive fine particles, etc.
1290 Chemical Products ", Chemical Daily, p. 875-
p. 876 and the like.

Further, as the filler, carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, Mg
CO ₃ , CaCO ₃ , ZnO, CaO, WS ₂ , MoS ₂ ,
MgO, SnO ₂ , Cr ₂ O ₃ , Al ₂ O ₃ , α-Fe
₂ O ₃ , α-FeO ₂ H, SiC, CeO ₂ , BN, Si
Inorganic fillers such as N, MoC, BC, WC, titanium carbide, corundum, artificial diamond, garnet, garnet, quartzite, triboli, diatomaceous earth, dolomite, polyethylene resin particles, fluororesin particles, guanamine resin particles, acrylic resin Organic fillers such as particles, silicon resin particles, and melamine resin particles can be used.

The amount of these various additives is usually from 0 to 20.
% By weight, more preferably 0 to 15% by weight.

The thickness of the color material layer is usually 0.1 to 5.0 μm.
It is more preferable that the thickness be in the range of 0.3 to 3.0 μm. Further, the color material layer may be formed as a single layer, and may have a multilayer structure having the same composition, or may have a different composition.
A multi-layer structure having more than two layers may be used.

The coloring material layer is kneaded with a binder resin and a coloring material, and, if necessary, a lubricant, a dispersant, an antistatic agent, a filler, a filler, and a solvent to form a high-concentration coloring material layer forming composition. After preparation, the composition for forming a high-concentration colorant layer is diluted to form a colorant-layer-forming composition for coating, coated on a support and dried to form a composition.

Organic solvents used in the paint for forming the color material layer and the protective layer described later include alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve), and aromatics (toluene, Xylene, chlorobenzene, etc.), ketones (acetone, methyl ethyl ketone, etc.), ester solvents (ethyl acetate,
Examples thereof include butyl acetate, ethers (tetrahydrofuran, dioxane, etc.), halogen solvents (chloroform, dichlorobenzene, etc.), amide solvents (eg, dimethylformamide, N-methylpyrrolidone, etc.). For the kneading and dispersion of the color material layer components, 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 color material layer can be formed on the support by, for example, coating and drying with an extrusion-type extrusion coater, which is the third means for obtaining a high-resolution image. The surface may be calendered to increase the hardness of the surface.

When the coloring material layer and the protective layer are provided, the coating and drying may be repeated for each layer, but the coating and drying may be performed in a wet-on-wet system and dried. In that case, it can be applied by a combination of a reverse roll, a gravure roll, an air doctor coater, a blade coater, an air knife coater, a squeeze coater, an impregnating coater, a bar coater, a transfer roll coater, a kiss coater, 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 remains wet, which is preferable because the adhesiveness between the upper and lower layers is improved.

As a means for further improving the image durability of the image forming material of the present invention, it is preferable to include fine particles in the coloring material layer or in at least one of the protective layers. Examples of the fine particles include colloidal silica, alumina sol, titania sol, and other metal oxide sols. The form of the metal oxide fine particles may be spherical, needle-like, feather-like, or any other form. Further, a surface treatment may be performed on the particle surface.

Non-porous metal oxide particles (silica,
Examples thereof include alumina, titania, zirconia, iron oxide, and chromium oxide), metal carbide particles (such as silicon carbide), boron nitride particles, and diamond particles.

The transfer sheet used in the present invention can be used as a transfer sheet by providing an adhesive layer on a resin film used as a support. 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, a hot solvent. And the like.

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.

The thickness of the sheet to be transferred is 0.5 to 100 μm.
Degree is preferred, more preferably 1 to 50 μm,
The thickness of the adhesive layer is preferably about 0.1 to 40 μm, and more preferably 0.3 to 30 μm.

The peeling force of the sheet to be transferred needs to be so close that unnecessary peeling does not occur due to the influence of bending or winding during transport in the apparatus before exposure. After the exposure, it is important that the transfer force be equal to or less than a peeling force of an apparatus for easily peeling the transfer sheet. For the above reason, the peeling force of the transfer sheet of the image forming material of the present invention is 1 in JIS C 2107 (JIS Z 0237).
In the 80-degree peeling method, 1 gf / c before image formation
m or more, and preferably 50 gf / cm or less when peeling after exposure.

In the present invention, the peeling force of the sheet to be transferred is ASTM (AMERICA SOCIETY FOR).
TESTING AND MATERIALS) D1
It is preferably from 2 to 15 gf / cm, more preferably from 3 to 10 gf / cm, according to a T-peeling method of 876-95.

As a method for peeling the transfer sheet from the image forming material, various peeling methods such as a peeling plate, a peeling roll fixing method using a peeling roll can be used as long as they do not affect the image formation. In order to reduce jams in the apparatus and reduce the size of the peeling mechanism, the peeling force must be 1
It is important that it is 0 g / cm or less. 10g / cm
If it exceeds, the stability in the peeling device becomes insufficient or the size of the device is increased.

When the adhesive layer of the transfer sheet used in the present invention is a heat-sensitive adhesive layer, the color material sheet and the transfer sheet are adhered and bonded by simultaneously performing heating and pressurization. When the adhesive layer is a pressure-sensitive adhesive layer, pressure is applied to bring the color material sheet and the transfer-receiving sheet into close contact with each other and to bond them. As a heating and pressing method in the bonding, a room temperature to about 180 ° C. with a heat roll, 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, room temperature to about 180 ° C., preferably 30 to 180 ° C.
At 150 ℃, 0.05~10kg / cm ^2, preferably about at a pressure of 0.5 to 5 kg / cm ^2, about 0.1 to 50 seconds, preferably heated 0.5-20 seconds.

One form of the protective layer used in the present invention is mainly composed of a binder resin and preferably comprises a crosslinking agent and additives such as fine particles.

Specific examples of the binder resin include polyurethane resins, polyester resins, vinyl chloride resins such as vinyl chloride-vinyl acetate copolymer, polyolefin resins such as butadiene-acrylonitrile copolymer, and polyvinyl resins such as polyvinyl butyral. Acetal resin, 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 butyral, polyvinyl acetoacetal And acetal-based resins such as 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.

The content of the binder resin in the protective layer is about 10 to 99.5% by weight, preferably 40 to 98% by weight in the protective layer forming component.

In order to enhance the durability of the protective layer, it is preferable to carry out crosslinking using a crosslinking agent such as polyisocyanate. As the binder resin selected when crosslinking the protective layer binder resin, it is preferable to use a resin having a functional group capable of undergoing a crosslinking reaction with a crosslinking agent in the molecule. Specifically, when an isocyanate-based crosslinking agent is used as the crosslinking agent, a phenoxy-based resin, an epoxy-based resin, a cellulose-based resin, an acetal-based resin, an acrylic resin, a urethane-based resin, a vinyl chloride-based resin, and a polyester-based resin are used. It is preferable to use such as.

The fine particles include carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, MgCO ₃ ,
CaCO ₃ , ZnO, CaO, WS ₂ , MoS ₂ , Mg
O, SnO ₂ , Al ₂ O ₃ , α-Fe ₂ O ₃ , α-FeO
₂ H, SiC, CeO ₂ , BN, SiN, MoC, BC,
Inorganic fillers such as WC, titanium carbide, corundum, artificial diamond, feldspar, garnet, quartzite, triboli, diatomaceous earth, dolomite, polyethylene resin particles, fluorine resin particles, guanamine resin particles, acrylic resin particles,
Organic fillers such as silicon resin particles and melamine resin particles are exemplified.

The fine particles and the organic resin particles may also serve as a release agent. Examples of the fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, and alumina.
Resin particles such as guanamine resin particles, acrylic resin particles, and silicon resin particles can be used.

The addition amount of these inorganic and organic resin particles is as follows:
Although it depends on the specific gravity, it is preferably 0.1 to 70% by weight.

In the image forming step, the protective layer in the present invention is imagewise exposed to image energy by irradiating it with heat energy, causing abrasion in the exposed portion of the colorant layer, and causing unnecessary colorant on the sheet to be transferred. In transferring the layer, the protective layer on the exposed portion of the colorant layer is transferred together onto the transfer sheet.

In the present invention, it is preferable to crosslink the colorant layer and the protective layer in order to enhance the durability of the image forming material. However, as one embodiment of the present invention, the crosslinking agent is used for coating the colorant layer and the protective layer. A curing agent is contained in one of the liquids, and both layers are cross-linked by transferring the cross-linking agent from the color material layer to the protective layer or from the protective layer to the color material layer during lamination coating or processing. And This eliminates the need to include a cross-linking agent in at least one side of the coating solution, thereby improving the temporal stability of the coating solution, that is, the pot life, without impairing image durability.

In order to transfer the cross-linking agent of the color material layer or the protective layer to another layer, when the coating liquid for the protective layer is applied on the color material layer, the color material is so degraded that the color material layer is not destroyed. Use a composition that can penetrate and swell in the layer, use a cross-linking agent that is soluble in the coating liquid for the protective layer in the colorant layer, or use a composition that allows the cross-linking agent itself to thermally diffuse during heat treatment. Is preferred. In particular, it is more preferable that the cross-linking agent is liquid at a temperature at which the image forming material is subjected to heat treatment, since this effect becomes remarkable. However, it is important to heat-treat the color material layer and the protective layer at the same time in order to diffuse the heat during the heat treatment. If only the color material layer is heat-treated first, not only the process becomes twice but also the transfer of the cross-linking agent occurs. It is not preferable because it becomes difficult.

For example, when the colorant layer coating solution uses water and the protective layer coating solution uses an organic solvent such as toluene or methyl ethyl ketone, the solvent is soluble in either coating solution such as a melamine crosslinking agent as a crosslinking agent. This is achieved by incorporating a good crosslinking agent into one side of the colorant layer coating liquid or the protective layer coating liquid.

In the present invention, other layers may be provided as long as the object of the present invention is not impaired. For example, the surface of the support opposite to the surface on which the color material layer is provided may have antistatic properties, transportability, A backing layer may be provided to secure sheet feeding prevention.

When the above-mentioned backing layer is provided, it is usually preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm.
It is preferred to be in the range of μm.

In the present invention, using a color material sheet in which a color material layer is laminated on a support, image exposure with laser light is performed from the support side, and bonding of the exposed portion of the support and the color material layer is performed. In a preferred embodiment, after the force is reduced, the color material sheet and the transfer sheet are peeled off, and the exposed portion of the color material layer is transferred to the transfer sheet to form an image.

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

The image exposure can be used without any particular limitation as long as the light source can reduce the bonding force between the support and the colorant layer. Among them, in order to obtain a high resolution, an electromagnetic wave whose energy application area can be narrowed down, in particular, an ultraviolet ray having a wavelength of 1 nm to 1 mm, a visible ray, and an infrared ray are preferable. As a light source to which such light energy can be applied, for example, Examples 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, and a high-pressure mercury lamp. 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.

As the laser light source used in the present invention, generally known ruby laser, YAG
Solid lasers such as lasers and glass lasers;
Gas lasers such as Ne laser, Ar ion laser, Kr ion laser, CO ₂ laser, CO laser, He-Cd laser, N ₂ laser, excimer laser; InGaP laser, AlGaAs laser, G
aAsP laser, InGaAs laser, InAsP
Lasers, semiconductor lasers such as CdSnP ₂ lasers and GaSb lasers; chemical lasers, dye lasers, and the like. Among them, in order to cause ablation efficiently, a laser having a wavelength of 600 to 1200 nm is used. Since light energy can be converted to heat energy, it is preferable in terms of sensitivity.

[0069]

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

Example 1 <Image Forming Material> An image forming material of the present invention and a comparative example were produced using a support, a coloring material layer, a protective layer, and a transfer sheet shown below.

Sample 1 (Coloring material layer C1) The following composition was kneaded and dispersed using an open kneader to prepare a coating material for forming a coloring material layer, which was applied on a support by extrusion coating, and then dried. And then subjected to a surface treatment with a calender to form a coloring material layer having a coating amount of 2.5 g / m ² .

-Colorant layer coating liquid- Fe-Al based ferromagnetic metal powder (colorant and metal-containing powder) (Fe: Al atomic ratio = 100: 4 (whole), 50:50 (surface) average) 100 parts Polyester / urethane resin (Toyobo Co., Ltd .: Byron UR 8300, solid content 30%) 30 parts Polyester / urethane resin (Toyobo Co., Ltd .: Byron UR) 4122, solid content 30%) 15 parts Polyester resin (manufactured by Toyobo Co., Ltd .: Byron 28SS, solid content 30%) 5 parts α-alumina (average particle diameter 0.15 μm) 5 parts stearic acid 1 part stearic acid Butyl 1 part Cyclohexanone 100 parts Methyl ethyl ketone 100 parts Toluene 100 parts (Protective layer P1) A protective layer coating solution comprising the following composition was prepared and coated with a wire bar. After coating on the surface of the colorant layer, it was dried to form a protective layer having a coverage of 0.2 g / m ² .

<Protective Layer Forming Coating Solution 1> Phenoxy resin [Phenoxy Associates, Phenoxy resin PKHH] 3.0 parts Polyester resin [Elitel UE3690, manufactured by Unitika Ltd.] 3.65 parts Polyethylene wax dispersion (solid (15% by weight) [Micro flat CE-155, manufactured by Koyo Chemical Co., Ltd.] 2.33 parts Toluene 120.0 parts Cyclohexanone 80.0 parts (Transfer sheet) 1) 25 μm easy-adhesion as a transfer sheet Using a layer-treated transparent polyethylene terephthalate film (T-100E, manufactured by Diafoil Hoechst Co., Ltd.), an adhesive layer forming coating solution having the following composition was applied onto this easily-adhesive treated surface and dried. An adhesive layer of 3 g / m ² was formed. Next, the adhesive surface of the transfer-receiving sheet with the adhesive layer and the side surface of the color material layer were faced, and the surface temperature was 75 ° C.
Pressure roll heated to [Rubber hardness 70, rubber thickness 8m
m, diameter 50 mm, transfer speed; 30 mm / sec, pressure 2.
0 kg / cm], and a pressure treatment is carried out so that air bubbles do not enter, and a color material layer and a transfer-receiving sheet are laminated on the support in this order, and the peeling force is adjusted to be 3 g / cm or more and 8 g / cm or less. Thus, an image forming material was prepared.

Polyurethane resin (solid content 21%) 40 parts [Nipporan 3109, manufactured by Nippon Polyurethane Industry Co., Ltd.] Silicone resin fine particles 0.2 parts [Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.] Methyl ethyl ketone 25.0 parts Toluene 25 1.0 part Cyclohexanone 15.0 parts Sample 2 The color material layer in Sample 1 was changed to the following composition, and immediately after coating the color material layer, before being coated with the protective layer, it was left in a 60 ° C. environment for 72 hours to heat the color material layer. After the treatment and further application of the protective layer, 60
An image forming material was prepared in the same manner as above except that the color material layer and the protective layer were subjected to heat treatment for 72 hours in an environment of ° C.

-Coloring material layer C2-The following composition was kneaded and dispersed using an open kneader,
A coloring material layer forming coating solution containing a magnetic powder composed of a metal is prepared, applied on a support by extrusion coating, subsequently dried, and then subjected to a surface treatment with a calender to obtain a coating amount of 2.5 g. / M ² .

-Colorant Layer Coating Liquid- Fe.Al-based ferromagnetic metal powder (colorant and metal-containing powder) (Fe: Al atomic ratio = 100: 4 (overall), 50:50 (surface) average) 100 parts Polyester / urethane resin (Toyobo Co., Ltd .: Byron UR 8300, solid content 30%) 30 parts Polyester / urethane resin (Toyobo Co., Ltd .: Byron UR) 4122, solid content 30%) 15 parts Polyester resin (manufactured by Toyobo Co., Ltd .: Byron 28SS, solid content 30%) 5 parts α-alumina (average particle diameter 0.15 μm) 5 parts stearic acid 1 part stearic acid Butyl 1 part Polyisocyanate compound (Nippon Polyurethane Industry Co., Ltd .: Coronate HX) 1 part Cyclohexanone 100 parts Methyl ethyl ketone 100 parts Toluene 100 parts Trial 3 except that the protective layer coating liquid of the sample 2 was changed to below were prepared Sample 3 similarly.

-Protective layer P2- <Protective layer forming coating liquid 2> Polyester resin (solid content 30% by weight) [Pesthresin A-515G, manufactured by Takamatsu Oil & Fat Co., Ltd.] 10 parts Wax dispersion (solid content 35% by weight) 2 parts Crosslinking agent [CAT-A2, manufactured by Takamatsu Yushi Co., Ltd.] 0.5 parts Pure water 15 parts Sample 4 Changed the color material layer of Sample 3 to the following A sample 4 was prepared in the same manner except that

-Coloring material layer C3- A coloring material layer-forming coating solution comprising the following composition was prepared, applied on a support by wire bar application, and subsequently dried to obtain a coating amount of 2.5 g. / M ² .

Carbon black Polyvinyl alcohol aqueous solution dispersion (solid content: 15%) [FUJI SP BLACK 8031 manufactured by Fuji Dye Co., Ltd.] 100 parts Crosslinking agent Melamine resin [Sumitose Chemical Sumirezu 613 (80 wt% aqueous solution)] 4 parts Reaction accelerator [ACX-P (35 wt% aqueous solution, manufactured by Sumitomo Chemical)] 0.9 part Sample 5 In Sample 4, the protective layer P2 was changed to P1 and the coating material for forming a color material layer was applied immediately after the coating, and the protective layer was not heated. Was prepared in the same manner as above except that was laminated and applied.

Sample 6 Sample 6 was prepared in the same manner as in Sample 5, except that the color material layer was changed as follows.

-Coloring material layer C4- Carbon black Acrylic resin aqueous dispersion (solid content 27%) [FUJI SP BLACK 8051 manufactured by Fuji Dye Co., Ltd.] 55 parts Crosslinking agent Melamine resin [Sumitomo Chemical Sumirezu 613 (80 wt% aqueous solution) 3.5 parts Reaction accelerator [ACX-P (35 wt% aqueous solution, manufactured by Sumitomo Chemical)] 0.7 parts Pure water 45 parts Sample 7 Sample 7 was prepared in the same manner except that the coloring material layer of Sample 5 was changed as follows. Produced.

—Coloring Material Layer C5—Carbon Black Dispersion in Polyvinyl Alcohol Aqueous Solution (Solid Content 15%) [FUJI SP BLACK 8031 manufactured by Fuji Dye Co., Ltd.] 100 parts Pure water 5 parts Sample 8 Sample 8 was coated with a protective layer coating solution. Sample 8 was prepared in the same manner except for the following changes.

-Protective layer P3- <Protective layer forming coating liquid 3> Phenoxy resin [Phenoxy resin PKHH, manufactured by Phenoxy Associates] 3.0 parts Polyester resin [Elitel UE3690, manufactured by Unitika Ltd.] 3.65 parts Polyethylene Wax dispersion (solid content: 15% by weight) [Microflat CE-155, manufactured by Koyo Chemical Co., Ltd.] 2.33 parts Polyisocyanate compound (solid content: 75%) [Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.] 4.0 parts Toluene 120.0 parts Cyclohexanone 80.0 parts Sample 9 Sample 9 was prepared in the same manner except that the coating liquid for the protective layer of Sample 5 was changed as follows.

-Protective layer P4- <Protective layer forming coating liquid 4> Phenoxy resin [Phenoxy Associates, phenoxy resin PKHH] 3.0 parts Polyester resin [Elitel UE3690, manufactured by Unitika Ltd.] 3.65 parts Polyethylene Wax dispersion (solid content: 15% by weight) [Microflat CE-155, manufactured by Koyo Chemical Co., Ltd.] 2.33 parts Toluene 120.0 parts Cyclohexanone 80.0 parts Sample 10 Sample 5 was coated with a protective layer coating solution. Sample 10 was prepared in the same manner except that the following was changed.

-Protective layer P5- <Protective layer forming coating liquid 5> Phenoxy resin [Phenoxy resin PKHH, manufactured by Phenoxy Associates Co., Ltd.] 3.0 parts Polyester resin [Elitel UE3690, manufactured by Unitika Ltd.] 3.65 parts Inorganic Microparticles Synthetic silica 0.5 parts [Shilton AMT-SILICA # 100B, manufactured by Mizusawa Chemical Co., Ltd. Particle size: 1. 0 μm] Polyethylene wax dispersion (solid content: 15% by weight) [Microflat CE-155, manufactured by Koyo Chemical Co., Ltd.] 2.33 parts Toluene 120.0 parts Cyclohexanone 80.0 parts (Evaluation of applicability) Each sample In the preparation step, the coating solution for the protective layer was applied on the color material layer application surface with a wire bar, and the coated surface after drying was observed and evaluated according to the following criteria.

Good with no coating unevenness and no coating flaws △ Degraded surface gloss or pinhole-shaped flaws × Streaked transmission flaws in color material layer <Image formation> Semiconductor laser (manufactured by Dainippon Screen Mfg. Co., Ltd.) : TCP-1080, dominant wavelength 830 nm), focusing on the color material layer, and 320 mJ / from the color material layer support side.
An image was formed by performing a scanning exposure with an energy of cm ² , performing solid exposure on the entire surface, and transferring an unnecessary colorant layer at an exposed portion to a transfer-receiving sheet. Next, the image-exposed portion was transferred to the transfer-receiving sheet side by peeling off at the interface between the color material layer of the image forming material and the transfer-receiving sheet (peeling angle: 90 °, peeling speed: 40 mm / sec) to form an image.

(Evaluation of residual density Dmin. At the exposed portion) After forming the image, the transmission density (OD: measured transmission density-transmission density of the support itself) of the image forming material at the exposed portion was measured with a densitometer [X-
The product was measured using the visual density of X-rite 310TR], and evaluated according to the following criteria.

◎ 0.025 or more and less than 0.035 ○ 0.035 or more and less than 0.045 △ 0.045 or more and less than 0.100 × 0.100 or more (Evaluation of abrasion) Two unexposed portions of each sample Cut and face each other, fix the lower sample on the desk, attach an iron weight of 100 g to the support surface side of the upper sample with double-sided tape, perform a rubbing test under the following conditions, and the state of each material after rubbing Was observed and evaluated according to the following criteria.

Number of times of rubbing: 20 reciprocations Speed: 200 mm / sec Moving distance 100 mm ◎ Traces of rubbing are seen on the surface but no penetrating scratches are observed ○ There are few pinhole-like scratches that can be observed with a 10x loupe △ A linear transmission scratch and a pinhole transmission scratch observed visually were observed. × A linear scratch visually observable occurred on half or more of the abraded surface. The results are shown in Table 1.

[0090]

[Table 1]

[0091]

The ablation image forming material of the present invention is excellent in production stability and excellent in durability and image quality of the obtained image.

Claims (11)

[Claims] 1. An ablation image forming method comprising: a support having a colorant layer containing a water-soluble or water-dispersible binder resin and a colorant on a support; and a protective layer containing an organic solvent-soluble binder resin. material. 2. The ablation image forming material according to claim 1, wherein the color material layer contains a polyvinyl alcohol resin or a polyvinyl acetal resin as a water-soluble binder resin, and carbon black or graphite as a color material. 3. A support comprising a color material layer having a binder resin and a color material which can be cross-linked by a cross-linking agent on a support, and a protective layer having a cross-linking agent which cross-links the binder resin and the binder resin in the color material layer. An ablation image forming material characterized by the following. 4. The ablation image forming material according to claim 3, wherein the cross-linking agent of the protective layer is a liquid at a temperature at which heat treatment is performed. 5. A color material layer having a binder resin, a color material and a cross-linking agent on a support, and a protective layer having a binder resin cross-linkable by the cross-linking agent. An ablation image forming material, wherein a binder resin can be crosslinked. 6. The ablation image forming material according to claim 5, wherein the cross-linking agent of the color material layer is liquid at a temperature at which heat treatment is performed. 7. The method according to claim 1, wherein the transfer sheet exhibiting adhesiveness by heat or pressure faces the protective layer surface side and is adhered releasably by heat or pressure.
7. The ablation image-forming material according to 4, 5 or 6. 8. The method according to claim 1, wherein at least one layer selected from a color material layer and a protective layer contains fine particles different from the color material. Ablation imaging material. 9. A colorant layer coating solution having a binder resin crosslinkable by a crosslinker on a support, a crosslinker and a colorant,
Ablation characterized by coating a protective layer coating solution having a binder resin and a crosslinking agent which can be crosslinked by a crosslinking agent on a support in this order and drying the coating, followed by heat treatment to simultaneously crosslink the colorant layer and the protective layer. A method for producing an image forming material. 10. An image forming material having a binder resin crosslinkable by a crosslinker and a colorant layer having a colorant provided on a support, and a protective layer having a binder resin and a crosslinker laminated thereon is heated. A process for producing an ablation image forming material, wherein a cross-linking agent of a protective layer is transferred into a color material layer by performing a treatment, and a binder resin of the color material layer is cross-linked. 11. An image forming material in which a colorant layer having a binder resin, a colorant and a crosslinking agent is provided on a support, and a protective layer having a binder resin which can be crosslinked by the crosslinking agent is laminated thereon. A method for producing an ablation image forming material, wherein a cross-linking agent of a color material layer is transferred into a protective layer by performing a treatment, and a binder resin of the protective layer is cross-linked.