JP2000158810A - Image forming material and method for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To perform ablation type recording having little damage and excellent durability of a formed image by sequentially forming an image forming layer and a protective layer having a specific static frictional coefficient or below on a transparent support in this order. SOLUTION: An image forming layer on a transparent support has fine particles, a binder resin and various type additives to be added as needed. As the particles, color material fine particles for bringing about an ablation by efficiently converting a laser beam into a heat are preferable in view of stability and a cost. Further, a protective layer is formed on the forming layer, and the protective layer uses a binder resin having a static frictional coefficient of 0.4 or below. A content of the binder resin is preferably about 40 to 98 wt.% in a protective layer forming component. Then, a light is emitted in an image- like state from a transparent support side, an ablation is brought about at an exposure part, and an image can be formed on the support. Thus, image durability can be improved while holding high sensitivity and image performance of high quality.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, light energy such as a laser beam is focused to irradiate a recording material to melt, deform, scatter, burn or evaporate a part of the material (hereinafter, these are collectively abbreviated as ablation). A recording method is known. These are dry treatments that do not require treatment liquids such as chemicals, and have the advantage that high contrast can be obtained by melting and deforming only the light irradiation part, scattering or evaporating and removing, and resist materials, It is used as an optical recording material such as an optical disk, a transparent original at the time of producing a printing plate, and the like.

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

However, when the above-described image forming material is used, there is a case where there is a problem of image durability. In order to improve such a problem, for example, Japanese Patent Application Laid-Open No. 60-25 / 1985
No. 5491, No. 61-061895, No. 61-199
No. 990, No. 61-206691, No. 62-2349
No. 91, JP-A-10-151860 and the like propose an image forming material in which a protective layer is laminated on an image forming layer.

[0005] By using such a material, the durability of the image can be greatly improved. However, even when the material is used for a transparent original or the like at the time of producing a printing plate, the material may be damaged.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to provide an ablation-type image-forming material having less scratches and excellent durability of a formed image, and an image-forming material using the same. It is to provide a method.

[0007]

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

(1) An ablation-type image forming material comprising an image forming layer and a protective layer having a static friction coefficient of 0.4 or less in this order on a transparent support.

(2) An image forming method, which comprises irradiating the image forming material according to the item (1) with light to cause ablation to form an image.

That is, the present inventors have found that by setting the static friction coefficient of the protective layer to 0.4 or less, it is possible to significantly improve image durability while maintaining high sensitivity and high quality image performance. This has led to the present invention. Hereinafter, the present invention will be described in detail.

<Method of Measuring Static Friction Coefficient> In the present invention, it is essential that the overcoat layer has a static friction coefficient of 0.4 or less. The static friction coefficient (μs) in the present invention is J
It can be determined by the same principle as the friction coefficient test method described in IS K7125. After leaving the ablation recording material for 1 hour or more under the condition of 25 ° C. and 60% RH, a constant load (contact force: F) is applied to a steel ball (eg, 0.5 to 5 mm in diameter).
p-example, 50-200 g) and apply a constant speed (eg, 20-100 cm / m) to the surface of the ablation recording material.
in), the initial maximum load (static friction force) (Fs) at that time is measured, and it is obtained by the following mathematical formula.

Μs = Fs / Fp μs: Coefficient of static friction Fs: Static frictional force N ｛kgf｝ Fp: Contact force N｝ kgf｝ For example, HEIDON [T
YPE 14DR].

The following is an example of a configuration effective for reducing the static friction coefficient of the protective layer to 0.4 or less, but the present invention is not limited to these.

For the protective layer, a binder resin is used. The binder resin can be used without any particular limitation as long as it can sufficiently hold the additive and the filler. Examples of such a binder resin include polyurethane, polyester, vinyl chloride resins such as vinyl chloride copolymers, vinyl chloride resins such as vinyl chloride-vinyl acetate copolymers, and polyolefin resins such as butadiene-acrylonitrile copolymers. Resins, polyvinyl acetal resins such as polyvinyl butyral, cellulose resins such as nitrocellulose, styrene resins such as styrene-butadiene copolymer, acrylic resins such as polymethyl methacrylate,
Acetal resins such as polyamide, phenolic resin, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl acetoacetal, and polyvinyl formal,
There are 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 from 10 to 99.5 in the components for forming the image protective layer.
% By weight, preferably 40 to 98% by weight. When curing the protective layer, it is preferable to use a resin having a functional group capable of undergoing a crosslinking reaction with a curing agent in the molecule as a binder selected. Specifically, when using an isocyanate-based curing agent as a curing agent, a phenoxy-based resin,
It is preferable to use an epoxy resin, a cellulose resin, an acetal resin, an acrylic resin, a urethane resin, a vinyl chloride resin, a polyester resin, or the like.

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

The protective layer of the image forming material of the present invention preferably contains at least one additive (lubricant) among waxes, silicon compounds and fluorine compounds.

Specific examples of the wax include solid waxes such as beeswax, candelilla wax, paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax and microcrystalline wax.

Specific examples of the silicon-based compound (including a wax-like compound) include straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, olefin-modified silicone oil, and polyether-modified silicone. Oil, epoxy-modified silicone oil, epoxy / polyether-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, phenol-modified silicone oil, mercapto-modified silicone oil, carboxy-modified silicone oil, higher fatty acid-modified silicone oil Radical reactive silicone oils such as silicone oil modified with carnauba, silicone oil modified with amide, silicone oil modified with (meth) acrylic, And it can include terminal reactive silicone oil such as silicone diamine, a halogen group, an alkoxy group, an ester group, an amide group, an organic modified silicone oil modified with an imide group or the like.

Examples of the fluorine-based compound include fluorine-based resins such as polytetrafluoroethylene, tetrafluoroethylene copolymers (eg, alkyl vinyl ether, ethylene, etc.), polyvinylidene fluoride, fluoroalkyl methacrylate, and fluororubber; Low molecular weight fluorine compounds such as ether oil, fluorine alcohol, fluorine carboxylic acid, perfluoroalkyl carboxylate, perfluoroalkyl quaternary ammonium salt, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide (adduct), perfluoroalkyl oligomer And the like. The amount of each of these materials is preferably from 0.1 to solid content in the protective layer.
30 wt%, more preferably 0.5 to 20 wt%
%. When multiple additions are made, the value is a multiple of this.

The protective layer preferably contains a matting agent in order to improve the adhesion of fingerprints by sebum and the ease of handling after image formation.

As the matting agent, carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, MgC
O ₃ , CaCO ₃ , ZnO, CaO, WS ₂ , MoS ₂ , M
gO, SnO ₂ , Al ₂ O ₃ , α-Fe ₂ O ₃ , α-FeO
OH, SiC, CeO ₂ , BN, SiN, MoC, B
Inorganic fillers such as C, WC, titanium carbide, corundum, artificial diamond, garnet, garnet, quartzite, triboli, diatomaceous earth, dolomite, polyethylene resin particles, fluororesin particles, guanamine resin particles, acrylic resin particles, silicon resin particles And organic fillers such as melamine resin particles.

Further, examples of the matting agent include inorganic fine particles and organic resin particles, which may also serve as a releasing agent. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, and alumina.Examples of the organic fine particles include fluorine compound particles, guanamine resin particles, acrylic resin particles, and silicon compound particles. Resin particles can be used. These inorganic / organic resin particles differ depending on the specific gravity, but are preferably added in an amount of 0.1 to 70% by weight.

The matting agent preferably has a narrow particle size distribution and a uniform particle size. Specifically, Toshiba Silicone Co., Ltd., silicone resin fine particles (product name Tospearl)
And Soken Chemical Co., Ltd., a crosslinked acrylic fine powder MR series, a crosslinked polystyrene fine powder SGP series, an acrylic ultrafine powder MP series, and a product of Fuji Silysia Chemical Ltd. (product name: Silo Hobic).

The average particle size r of the matting agent is preferably 0.3
μm or more and 20 μm or less, more preferably 0.8 μm
m or more and 4.5 μm or less.

The amount of the matting agent per unit area, the so-called sticking amount, is preferably from 5 mg / m ^{2 to} 150 mg / m ² , more preferably from 10 mg / m ^{2 to} 100 mg.
/ M ² or less.

When the surface of the matting agent has a polymerizable functional group, the adhesion between the image forming layer and the fine particles is improved during the curing of the image forming layer, so that the image durability is further improved.

The protective layer of the present invention has a thickness of 0.03 to 1.0.
μm is preferred, more preferably 0.05 to 0.8 μm, and particularly preferably 0.1 to 0.4 μm.

In order to apply the coating solution prepared by dissolving and / or dispersing the protective layer forming component, an extrusion-type extrusion coater, reverse roll coater, gravure roll coater, air doctor coater, blade coater, air knife, etc. Coater, squeeze coater,
Various known coater stations such as an impregnating coater, a bar coater, a transfer roll coater, a kiss coater, a cast coater, and a spray coater can be appropriately selected and used. Among these coaters, the coating of the protective layer is not particularly limited as long as the image forming layer is not damaged, but when the thickness of the protective layer is small, the coating in the above-described coater station is performed. Preferably, a material suitable for thin-layer coating is used, and an extrusion-type extrusion coater, a gravure roll coater, a bar coater, or the like can be used. In addition, when using a coating method such as a gravure roll coater or a bar coater that contacts the image forming layer, the rotation direction of the gravure roll or the bar may be either forward or reverse with respect to the transport direction, and In the case of forward rotation, a constant speed or a peripheral speed difference may be provided. Furthermore, when using a contacting coating method, an image forming layer to be described below is subjected to a smoothing treatment such as a calendar treatment after coating, or an image forming layer is coated and then cured and heat-cured. Is preferred. It is preferable to add a fatty acid to the protective layer of the present invention.

The fatty acid may be a monobasic acid or a dibasic acid, and preferably has 6 to 30 carbon atoms.
~ 22 is more preferable. Specifically, stearic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid,
Linolenic acid, oleic acid, elaidic acid, behenic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,1,
2-dodecanedicarboxylic acid, octanedicarboxylic acid and the like can be mentioned.

Examples of the fatty acid ester include oleyl oleate, isostil stearate, dioleyl alate, butyl stearate, butyl palmitate, butoxyethyl stearate, butoxyethyl palmitate, butyl myristate, octyl myristate, octyl palmitate , Pentyl stearate, pentyl palmitate, isobutyl oleate, stearyl stearate, lauryl oleate, octyl oleate, isobutyl oleate, ethyl oleate, isotridecyl oleate, 2-ethylhexyl stearate, 2-ethylhexyl palmitate, isopropyl palmitate, isopropyl Myristate, butyl laurate, cetyl-2-ethylhexarate, dioleyl adipate, diethyl adipate, diisobutyl adipate Over DOO, diisodecyl adipate, oleyl stearate, 2-ethylhexyl myristate, isopentyl myristate, isopentyl stearate, diethylene glycol - mono - ether palmitate, diethylene - mono - ether palmitate and the like.

It is preferable to add an abrasive to the protective layer of the present invention. The abrasive is preferably present as primary particles in the protective layer. For kneading and dispersion, two-roll mill, three-roll mill, ball mill, pebble mill, cobol mill, tron mill, sand mill, sand grinder, Sqeg
A vari attritor, a high-speed impeller disperser, a high-speed stone mill, a high-speed impact mill, a disper, a high-speed mixer, a homogenizer, an ultrasonic disperser, an open kneader, a continuous kneader, and the like can be appropriately selected and used. As the abrasive, inorganic oxides, inorganic nitrides, and inorganic carbides that are stable to the coating solvent and have high hardness of the fine particles themselves and are widely used as the abrasive are preferable.

The average particle size r of the abrasive is preferably 0.01
μm or more and 1 μm or less, more preferably 0.05 μm
m or more and 0.5 μm or less.

The transparent support used for the image forming material includes acrylates, methacrylates, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, nylon And resin films of aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, etc., and resin films obtained by laminating two or more layers of the above resins.

The support is preferably stretched into a film and heat-set in view of dimensional stability. Further, in the present invention, when the image forming method described below is performed, a laser beam is exposed imagewise from the support side, and therefore, one having a high transmittance with respect to the effective wavelength of the energy light is preferable.
% Or more, more preferably 80% or more. Incidentally, fillers such as titanium oxide, zinc oxide, barium sulfate, calcium carbonate and the like 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 it is 25 to 250 μm.

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

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

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

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

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

The shape of the ferromagnetic metal powder is preferably acicular with a major axis diameter of 0.30 μm or less, preferably 0.20 μm or less. By using such a ferromagnetic metal powder, the surface of the image forming layer can be formed. Performance can be improved.

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

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

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

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

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

When ferromagnetic metal powder is used as the coloring material fine particles, considering the liquid stability of the coating solution for the image forming layer, -SO ₃ M and -OSO _{3 are} contained in the binder resin.
At least one selected from M, —COOM and —PO (OM ₁ ) ₂ [where M represents a hydrogen atom or an alkali metal, and M ₁ represents a hydrogen atom, an alkali metal or an alkyl group]
It is preferable to have a kind of polar group since the dispersibility of the ferromagnetic metal powder can be improved. The content of the binder resin is 1 to 50% by weight of the image forming layer forming component.
Degree, preferably 5 to 60% by weight.

When a contact-type gravure coater or bar coater is used as a coater for coating the protective layer, the image forming layer is provided with a protective layer other than the coloring material fine particles for the purpose of preventing the image forming layer from being scraped off. Inorganic fine particles added to the
It is preferable to contain fine particles such as organic fine particles and fluorine compounds, and it is more preferable to add an abrasive added to the protective layer.

For the purpose of reducing protrusions on the surface of the image forming layer, the content of such an abrasive is preferably 15% by weight or less in the composition for forming an image forming layer.

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

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

Examples of the lubricant include a fatty acid, a fatty acid ester, a fatty acid amide, a (modified) silicone oil, a (modified) silicone resin, a fluororesin, a carbon fluoride, and a wax, which are also added to the protective layer. Can,
Examples of the dispersant include fatty acids having 12 to 18 carbon atoms, such as lauric acid and stearic acid, and amides, alkali metal salts, and alkaline earth metal salts thereof; polyalkylene oxide alkyl phosphates, lecithin, trialkyl polyolefinoxy Quaternary ammonium salts; and azo compounds having a carboxyl group and a sulfone group.

Examples of the antistatic agent include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a polymer antistatic agent, and conductive fine particles.

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

The thickness of the image forming layer is 0.05 to 5.0 μm.
m, preferably in the range of 0.1 to 3.0 μm.
Further, the image forming layer may be composed of a single layer or a multilayer having different compositions.

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

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

The thickness of the release sheet is about 6 to 100 μm,
Preferably it is 10 to 50 μm, and the thickness of the adhesive layer is 0.1 μm.
It is about 0.5 to 30 μm, preferably 0.1 to 20 μm. In the case where a release sheet provided with an adhesive layer is used, the release sheet can be provided on a release sheet support in the same manner as the protective layer.

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

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

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

The image exposure with a laser beam can be used without any particular limitation as long as it is a light source which ablates at the interface between the transparent support and the image forming layer. Electromagnetic waves whose energy application area can be narrowed down, in particular, ultraviolet rays, visible rays, and infrared rays having a wavelength of 1 nm to 1 mm are preferable. As such laser light sources, generally known ruby lasers and YAGs
Laser, glass laser, etc .; solid state laser; He-N
e laser, Ar ion laser, Kr ion laser, CO ₂ laser, CO laser, He-Cd laser, N ₂ laser, gas laser such as excimer laser; InGaP laser, AlGaAs laser, Ga
Semiconductor lasers such as AsP laser, InGaAs laser, InAsP laser, CdSnP ₂ laser, and GaSb laser; chemical lasers, dye lasers, and the like; The use of a 1200 nm laser is preferable in terms of sensitivity since light energy can be converted to heat energy.

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

The ablation referred to here means that the image forming layer and the protective layer are completely scattered by a physical or chemical change, a part of the image forming layer and the protective layer are destroyed and / or scattered. This includes a phenomenon in which only the formation layer is destroyed and a physical or chemical change occurs only near the interface between the image formation layer and the transparent support or the intermediate layer. In addition, as a method of peeling the exposed image forming material, a peeling plate, a peeling angle fixing method using a peeling roll, a hand peeling method of peeling off the peeling sheet and the image forming material without fixing by hand, and the like, affect the image formation. Otherwise, various stripping methods can be used.

[0066]

EXAMPLES Example 1 (Sample Nos. 1 to 9) Hereinafter, the present invention will be described 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. The transmission density is a transmission density obtained by measuring a visible light transmission density using Xrite manufactured by X-rite.

The following image forming layer forming compositions were separately kneaded and dispersed by using a Henschel mixer and a sand mill, and then the obtained one liquid, two liquids and a polyisocyanate compound [Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd .; [Active ingredient 100%] in a weight ratio of 100: 2.39: 0.3.
7, and stirred with a dissolver to prepare a coating solution for forming an image forming layer.

The prepared coating solution for forming an image forming layer was dispersed in an ultrasonic wave, and then extruded by extrusion. The transparent polyethylene terephthalate film having a thickness of 100 μm and having one surface subjected to corona discharge treatment [Lumilar T60, manufactured by Toray Industries, Inc.] Coating and drying, then using a heat roll, temperature 100 ° C, linear pressure 150 kg / cm, transport speed 6
A calendar process is performed at 0 m / sec.
After aging for 0 hour, an image forming layer having a thickness of 1.33 μm was formed.

<Image Forming Layer Forming Composition> 1-part Ferromagnetic metal powder [MAP T1650SB, manufactured by Kanto Denka Kogyo KK] 100 parts Polyurethane resin [Byron UR4122, manufactured by Toyobo Co., Ltd.] 13.5 parts Phenoxy resin [Phenoxy resin PKHH, manufactured by Phenoxy Associates] 1.5 parts Phosphate ester [Phosphanol RE610, manufactured by Toho Chemical Industry Co., Ltd.] 3.0 parts Methyl ethyl ketone 105.0 parts Toluene 105.0 parts Cyclohexanone 90.0 parts 2 parts Alumina [manufactured by Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 100 parts Polyurethane resin [manufactured by Toyobo Co., Ltd., Byron UR4122] 15 parts Methyl ethyl ketone 41.3 parts Toluene 41.3 parts Cyclohexanone 35.4 parts Protective layer forming coating solutions 1 to 9 having the following composition Using a sand mill to prepare, the reverse of a bar coater coating, after application and drying on the image forming layer, a further 60 ° C. 72
After aging for a time, a protective layer having a thickness of 0.25 μm was formed.

<Protective Layer Forming Coating Solution 1> UCAR Phenoxy Resin PKHH (manufactured by Union Carbide) 0.99 parts Elitel UE-3690 (manufactured by Unitika) 0.99 parts Coronate HX (Nippon Polyurethane Industry Co., Ltd.) 0.77 parts Polyethylene wax CE-155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Stearic acid 0.06 parts alumina [High-purity alumina HIT60G, manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Toluene 48.5 parts Cyclohexanone 48.5 parts <Protective layer forming coating liquid 2> UCAR phenoxy resin PKHH (manufactured by Union Carbide) 2.16 parts Silica [Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Polyethylene wax C E-155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Alumina [manufactured by Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 0.06 parts Stearic acid 0.06 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.6 part Toluene 48.5 parts Cyclohexanone 48.5 parts <Coating liquid 3 for forming protective layer> Elitel UE-3350 (manufactured by Unitika) 2.16 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Polyethylene wax CE-155 (Koyo Chemical Co., Ltd.) 0.06 parts Alumina [Sumitomo Chemical Co., Ltd., high-purity alumina HIT60G] 0.06 parts Stearic acid 0.06 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.6 parts Toluene 48.5 parts Cyclohexanone 48.5 parts <Coating liquid 4 for forming protective layer> Erie 1. UE3300 (manufactured by Unitika Ltd.) 2.16 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Polyethylene wax CE-155 (manufactured by Koyo Chemical Co., Ltd.) 06 parts Alumina [High purity alumina HIT60G, manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Stearic acid 0.06 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.6 parts Toluene 48.5 parts Cyclohexanone 48.5 Part <Coating liquid 5 for forming protective layer> Elitel UE-3600 (produced by Unitika Ltd.) 2.16 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts polyethylene wax CE-155 ( 0.06 parts Alumina [High purity alumina HIT60G, manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Stearic acid 0 0.06 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.6 parts Toluene 48.5 parts Cyclohexanone 48.5 parts <Protective layer forming coating liquid 6> Pandex T-5210 (Dainippon Ink Industries, Ltd.) 2.16 parts Silica [Silohobic 200, manufactured by Fuji Silysia Chemical Ltd.] 0.06 parts Polyethylene wax CE-155 (Koyo Chemical Co., Ltd.) 0.06 parts Alumina [Sumitomo Chemical Co., Ltd.] High purity alumina HIT60G] 0.06 parts Stearic acid 0.06 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.6 parts Toluene 48.5 parts Cyclohexanone 48.5 parts <Protective layer forming coating liquid 7>> Nipporan N-3109 (manufactured by Nippon Polyurethane Industry Co., Ltd.) 2.16 parts silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hovic 200] 0.06 parts Polyethylene wax CE-155 (manufactured by Koyo Chemical Co., Ltd.) 0.06 parts Alumina [High purity alumina HIT60G manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Stearic acid 0.06 parts Coronate HX (Japan Polyurethane Industry Co., Ltd.) 0.6 parts Toluene 48.5 parts Cyclohexanone 48.5 parts <Coating liquid 8 for forming protective layer> UCAR phenoxy resin PKHH (manufactured by Union Carbide Co.) 0.99 parts Elitel UE-3690 (Unitika) 0.99 parts Silica [Silohobic 200, manufactured by Fuji Silysia Chemical Ltd.] 0.06 parts Alumina [High-purity alumina HIT60G, manufactured by Sumitomo Chemical Co., Ltd.] 0.06 parts Stearic acid 0. 06 parts Coronate HX (Nippon Polyurethane Industry Co., Ltd.) 0.6 parts Toluene 48.62 parts Cyclohexanone 48.62 parts <Coating liquid 9 for forming protective layer> UCAR phenoxy resin PKHH (manufactured by Union Carbide) 2.16 parts Silica [manufactured by Fuji Silysia Chemical Ltd., Silo Hobic 200] 0.06 parts Alumina [Sumitomo Chemical High purity alumina HIT60G manufactured by Co., Ltd.] 0.06 parts Stearic acid 0.06 parts Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.6 parts Toluene 48.53 parts Cyclohexanone 48.53 parts Separately, 38 μm in thickness An adhesive layer composition having the following composition was applied to an easy-contact surface of a transparent polyethylene terephthalate film [T100E, manufactured by Diafoil Hoechst Co., Ltd.], which was easily treated on one side with a bar coater, and dried to a film thickness of 1.20 μm.
Was provided to produce a release sheet.

<Adhesive layer composition> Urethane resin [Nipporan 3109, manufactured by Nippon Polyurethane Industry Co., Ltd.] 4.90 parts Silicone resin particles [Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.] 0.10 parts Toluene 42.75 parts Methyl ethyl ketone 42.75 parts Cyclohexanone 9.50 parts Then, the protective layer surface of the above-mentioned image forming material and the adhesive layer surface of the release sheet were made to face each other, and heated and pressurized [roll temperature;
0 ° C., transport speed: 80 mm / sec, pressure 6.0 kg / cm
² ] to produce an integrated image forming material having a release sheet bonded thereto.

Using the image forming material prepared in this way, the focal point is adjusted to the interface between the transparent support of the image forming material and the image forming layer, and an EV laser proofer [PS data] is used using postscript data (PS data). Konica Corporation,
After exposing at a rotation speed of 425 rotations and a power of 100%], the substrate was peeled off, and the resolution, Dmin. (Dirt of the exposed part),
The scratch resistance was evaluated.

-Dmin. Evaluation of (Stain on Exposed Area)-A 0% halftone image was formed at a screen ruling of 175 lines, a halftone dot square, and a screen angle of 45 °, and the transmission density of the formed halftone image was measured at an arbitrary 30 points. Densitometer [Xr
It was measured using the visual density of X-rite 310TR manufactured by ITE, and the average density ODav was evaluated.

A: Average density is less than 0.050 O: Average density is 0.050 or more and less than 0.060 Δ: Average density is 0.060 or more and less than 0.075 ×: Average density is 0.075 or more.

-Evaluation of Resolution- An image is formed by using a vertical stripe pattern in the main scanning direction of a drum of 2000 DPI as PS data, and the formed vertical stripe pattern is arbitrarily extracted at 30 points in the main scanning direction, and the loupe is used in the sub scanning direction. And the difference in width between the exposed and unexposed portions was measured, and the average was evaluated.

：: Average of difference in width between exposed portion / unexposed portion is less than 1 μm ：: Average of difference in width between exposed portion / unexposed portion is 1 μm or more, 2
Less than μm Δ: The average of the difference in width between the exposed part and the unexposed part is 2 μm or more, and 4
Less than μm −Evaluation of scratch resistance− The area where the halftone dot image and the protective layer surface are in contact with the protective layer surface of each sample is 1 cm × 2 cm (width direction) After applying a load of 2 kg / cm and reciprocating 5 times at a transport speed of 50 cm / sec or a transport speed of 10 cm / sec and a transport distance of 20 cm, observe the rubbed surface to determine the degree of scratching. Evaluation was made according to the following criteria.

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

Table 1 shows the above results.

[0079]

[Table 1]

As shown in Table 1, when the coefficient of static friction was 0.4 or less (samples 1 to 5), scars reaching the colored layer were scarcely formed, and the coefficient of static friction was 0.4 or more (sample 6).
In the cases of (1) to (9), scratches reaching the colored layer are observed.

[0081]

According to the present invention, it has been possible to provide an ablation type image forming material which has few scratches, has a high resolution and is excellent in durability of a formed image, and an image forming method using the same.

Claims (2)

[Claims] 1. An ablation type image forming material comprising an image forming layer on a transparent support and a protective layer having a static friction coefficient of 0.4 or less in this order. 2. An image forming method, comprising: irradiating the image forming material according to claim 1 with light to cause ablation to form an image.