JPH1195449A - Image forming material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming material having high sensitivity and excellent image quality and an image forming method using the image forming material. SOLUTION: The image forming material has at least one layer of the image forming layers 2, 6 on bases 1, 5. At least one layer of these image forming layers are formed by dispersing metallic powder color materials capable of absorbing the wavelength light of an exposure light source into resin binders and the abrasion thereof is induced by the exposure with high-density energy light. The image forming material has back-coating layers 3, 7 having the glass transition point of the binder at >=75 deg.C on the surfaces having the image forming layers 2, 6 on the side opposite to the base surface. The image forming material is exposed with the high-density energy light to degrade the binding strength between the base and image forming layers of irradiated parts. Image formation is executed by removing the image forming layers of the irradiated parts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming material having high sensitivity and excellent image quality, and an image forming method using the image forming material.

[0002]

2. Description of the Related Art Hitherto, there has been known a recording method in which light energy such as a laser beam is focused and a material to be recorded is irradiated with light to cause a part of the material to be melt-deformed, fly away, burn or evaporate. I have. This method has an advantage that a high contrast can be obtained because it is a dry type that does not require a treatment liquid such as a chemical, and only the light irradiation part is melted or deformed or scattered or evaporated. For that purpose, various materials using this recording method have been proposed, and are used as resist recording materials, optical recording materials such as optical disks, and image forming materials which themselves are viewed as visualized images. These image forming methods are usually called ablation.

[0003] With respect to an image forming method by ablation, for example, Japanese Patent Application Laid-Open Nos.
No. 638, No. 62-115153, and the like, a method of forming a resist pattern by photodecomposing a binder resin by pattern exposure and a material therefor are disclosed in JP-A-55-13 / 1979.
No. 2536, No. 57-27788, No. 57-1031
Japanese Patent Application Laid-Open No. 64-56591, Japanese Patent Application Laid-Open No. 1-99887, and Japanese Patent Application Laid-Open No. 1-998787 disclose that an inorganic compound thin film provided by a vapor deposition method is exposed to light and the information is recorded by melting deformation of the film.
No. 4,016,163 discloses a material for recording information by removing a colored binder layer by photothermal conversion.
245,003 and the like each disclose an image forming material having an image forming layer containing graphite or carbon black.

Further, Japanese Patent Application Laid-Open No. Hei 4-506709, Japanese Unexamined Patent Publication No.
No. 43635, U.S. Pat. Nos. 5,156,938, 5,171,650, and 5,256,506 include a photothermal conversion material that absorbs laser light and converts it to heat energy, and heat. An image-forming material having an image-forming layer containing a decomposable binder resin as an essential component is described, among which JP-T4-506709, U.S. Pat. Nos. 5,156,938 and 5,171,650. Nos. 5,256,506 and the like receive an image forming layer from which a binder resin is decomposed and blown off by a transfer-receiving body, and according to these, an image scattered by ablation into the air. The scattering of the fine powder in the formation layer is improved.

However, in spite of variously devised configurations of the binder resin, the light-to-heat conversion compound, and the image forming material, it is difficult to obtain an image having a high transmission density and a high resolution. Is still inadequate.

[0006] In order to solve these problems, an image forming material by a laser ablation transfer method has been studied. In the laser ablation transfer method, image exposure is performed from the support side, and after the exposed color material layer is ablated from the support, the color material layer and the image receiving layer surface of the transfer sheet having the image receiving layer on the base material Are pressed against each other, and only the ablated color material layer is pulled out to the transfer sheet side to form an image.

However, when the conveying surface of the image forming material is smooth, the conveying property in the image forming apparatus is deteriorated,
Further, when printing on a PS plate using an image formed on the support, it takes time to adhere to the PS plate. The above problem can be solved by matting the conveying surface or the surface opposite to the image forming surface of the support. However, in the case of this image forming material, since laser exposure is performed from the support side, transmission of laser light by matting is performed. The rate is reduced and scattering occurs, and sensitivity and resolution are deteriorated.

In the case where this image forming material is used, if laser exposure is performed with dust or dust attached before forming an image, the color material layer at the exposed portion remains unexposed, and after the image is formed, the transfer sheet When the laser exposure is performed by the outer surface scanning method, the drum rotates at a high speed, making it easier to be charged. Or transport trouble in the apparatus. Furthermore, when a back coat layer is provided on the back surface of the support to solve the above problem, the image forming sheet having the color material layer on the support and the transfer-receiving sheet are closely adhered or bonded by applying heat. When a heat roll is used in the step of causing the heat roll, another problem arises in that the surface of the back coat layer directly in contact with the heat roll becomes cloudy or that a part of the back coat layer adheres to the heat roll.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an image forming material which has high sensitivity and image quality, and which is provided with an antistatic property, a transporting property and a heat resistance. An object of the present invention is to provide an image forming method used.

[0010]

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

(1) At least one image forming layer is provided on a support, and at least one of the image forming layers is formed by dispersing a metal powder coloring material capable of absorbing the wavelength light of an exposure light source in a resin binder. And an image forming material which undergoes ablation by exposure to high-density energy light, wherein a back coat layer having a glass transition point of a binder of 75 ° C. or higher is provided on the surface opposite to the support surface having the image forming layer. .

(2) At least one image forming layer is provided on the support, and at least one of the image forming layers is formed by dispersing a metal powder coloring material capable of absorbing the wavelength light of an exposure light source in a resin binder. And a polymer having a glass transition point of 75 ° C. or higher and a glass transition point of 75 ° C. on a surface of the image forming material which causes ablation by exposure to high-density energy light, opposite to the surface of the support having the image forming layer.
An image forming material having a back coat layer which is a mixed system of less than 10

(3) The image forming material according to (1) or (2), wherein the binder of the back coat layer is a polyester resin.

(4) The image forming material according to (1), (2) or (3), wherein the back coat layer contains at least one kind of lubricant.

(5) The image forming material according to (4), wherein one of the lubricants in the back coat layer is a wax.

(6) The image forming material according to (5), wherein the melting point of the wax is 80 ° C. or higher.

(7) The image forming material as described in any one of (1) to (6), wherein the back coat layer contains an antistatic agent.

(8) The image forming material according to any one of (1) to (7), wherein the back coat layer contains a filler.

(9) The surface resistivity of the back coat layer is 1
The image forming material according to any one of (1) to (8), which has a resistance of 0 ¹¹ Ω / m ² or less.

(10) The image forming material according to any one of (1) to (9), wherein the back coat layer has a smoother value of 7 to 200 mmHg.

(11) The image forming material according to any one of (1) to (10) is exposed to high density energy light,
An image forming method for forming an image by reducing a bonding force between a support of an irradiation unit and an image forming layer and removing the image forming layer of the irradiation unit.

(12) At least one image forming layer is provided on the support, and at least one of the image forming layers is formed by dispersing a metal powder coloring material capable of absorbing the wavelength light of an exposure light source in a resin binder. And an image forming material formed by facing an image forming layer surface of an image forming sheet which causes ablation by exposure to high-density energy light and an image receiving layer surface of a transfer receiving sheet having an image receiving layer; An image forming material having a back coat layer on the surface opposite to the support having the image forming layer and on the surface of the transfer receiving sheet opposite to the surface having the image receiving layer.

(13) The binder of at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet has a glass transition point of 75 ° C. or more.
2. The image forming material according to 1.

(14) The binder of at least one of the back coat layer of the image forming sheet and the back coat layer of the sheet to be transferred is a mixed system of a polymer having a glass transition point of 75 ° C. or lower and a polymer having a glass transition point of 75 ° C. or higher. There is (1
The image forming material according to 2).

(15) At least one binder of the back coat layer of the image forming sheet and the back coat layer of the sheet to be transferred is a polyester resin.
The image forming material according to 3) or (14).

(16) The image forming material according to any one of (12) to (15), wherein at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer-receiving sheet contains an antistatic agent.

(17) At least one of the back coat layer of the image forming sheet and the back coat layer of the transfer receiving sheet contains at least one kind of lubricant (12) to (1).
The image forming material according to any one of 6).

(18) One kind of lubricant is wax (1
The image forming material according to 7).

(19) The image forming material according to (18), wherein the melting point of the wax is 80 ° C. or more.

(20) The image forming material according to any one of (12) to (19), wherein at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet contains a filler.

(21) The smooth coat value of at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet is 7 to 200 mmHg.
(20) The image forming material as described in any one of (1) and (2) above.

(22) The image forming material according to any one of (12) to (21) is exposed to high-density energy light to reduce the bonding force between the support of the irradiated portion and the image forming layer, An image forming method for forming an image by removing an image forming layer of an irradiation section.

Hereinafter, the image forming material of the present invention will be described in detail.

<Image Forming Material> The image forming material of the present invention comprises, as a basic structure, an image forming sheet having an image forming layer (hereinafter referred to as a color material layer) on a support and a transfer sheet having an image receiving layer. A back coat layer is provided on the back surface of the support of the image forming sheet and / or the transfer sheet depending on the image form. Further, in order to improve image durability, a configuration having a protective layer on the color material layer is more preferable.

<Image forming sheet> As a support of the image forming sheet, acrylic acid ester, methacrylic acid ester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyvinyl chloride, polyethylene,
Polypropylene, polystyrene, nylon, aromatic polyamide, polyetheretherketone, polysulfone,
Examples include resin films such as polyethersulfone, polyimide, and polyetherimide, and transparent substrates such as resin films obtained by laminating two or more layers of the resin.

The support in the present invention is a support capable of transmitting 50% or more of light of the wavelength of the exposure light source, and is preferably stretched and heat-set into a film from the viewpoint of dimensional stability. Fillers such as titanium oxide, zinc oxide, barium sulfate, and calcium carbonate may be contained as long as they do not interfere. The thickness of the support is about 10 to 500 μm, preferably 25 to 250 μm.

The coloring material layer is basically composed of a coloring material and a binder resin for holding the coloring material. The colorant used in the present invention is a colorant capable of absorbing the wavelength light of the exposure light source. For example, carbon black is preferably used because it is a colorant having a wide absorption from the ultraviolet region to the visible and infrared regions. In addition, inorganic or organic pigments and dyes are used, and are composed of a single-color, two-color, or three-color pigment 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 near infrared, organic compounds such as cyanine, polymethine, azurenium, squarium, thiopyrylium, naphthoquinone and anthraquinone dyes, and phthalocyanine dyes can be used as near infrared light absorbers. , 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.

As a coloring agent that further exerts the effects of the present invention,
Metal atom-containing particles can be preferably used. When using metal atom-containing particles as a coloring agent, sensitivity, resolution,
The effect becomes more remarkable in improving the transmission density of the exposed portion. The term “metal atom-containing particles” is a general term for compounds such as metals such as iron, chromium, manganese, cobalt, nickel, copper, zinc, titanium, silver, aluminum, gold and platinum or oxides thereof.

The metal atom-containing particles preferably used in the present invention include ferromagnetic iron oxide powder, ferromagnetic metal powder, and cubic plate-like powder. Among them, ferromagnetic metal powder can be preferably used.

As the ferromagnetic iron oxide, γ-Fe ₂ O ₃ , F
e ₃ O ₄ or FeO _x (1.33 in these intermediate iron oxide <
x <1.50).
Examples of the ferromagnetic metal powder include Fe and Co, Fe-A
1 system, Fe-Al-Ni system, Fe-Al-Zn system, Fe
-Al-Co system, Fe-Al-Ca system, Fe-Ni system,
Fe-Ni-Al system, Fe-Ni-Co system, Fe-Ni
-Zn system, Fe-Ni-Mn system, Fe-Ni-Si system,
Fe-Ni-Si-Al-Mn system, Fe-Ni-Si-
Al-Zn system, Fe-Ni-Si-Al-Co system, Fe
-Al-Si system, Fe-Al-Zn system, Fe-Co-N
i-P system, Fe-Co-Al-Ca system, Ni-Co system,
Ferromagnetic metal powders such as metal magnetic powders mainly composed of Fe, Ni, Co, etc., are preferred. Among them, Fe-based metal powders are preferable. For example, Co-containing γ-Fe ₂ O ₃ , Co-adhered γ-F
Cobalt-containing iron oxide-based magnetic powders such as e ₂ O ₃ , Co-containing Fe ₃ O ₄ , Co-coated Fe ₃ O ₄ , and Co-containing magnetic FeO _x (4/3 <x <3/2) powder.

From the viewpoint of corrosion resistance and dispersibility, among Fe-based metal powders, Fe-Al-based, Fe-Al-Ca-based,
Fe-Al-Ni system, Fe-Al-Zn system, Fe-Al
-Co system, Fe-Ni-Si-Al-Co system, Fe-C
Preferred is an Fe-Al ferromagnetic powder such as an o-Al-Ca type. In this, the content ratio of Fe atoms to Al atoms contained in the ferromagnetic powder is Fe: Al = 10
0: 1 to 100: 20 and ESC of ferromagnetic powder
A (X-ray photoelectron spectroscopy) analysis depth 100Å
A compound having a structure in which the content ratio of Fe atoms and Al atoms existing in the following surface regions is Fe: Al = 30: 70 to 70:30 in atomic ratio, or Fe atoms, Ni atoms, and Al atoms Si atoms, furthermore Co atoms and at least one of Ca atoms are contained in the ferromagnetic powder, the content of Fe atoms is 90 atomic% or more, the content of Ni atoms is 1 to 10 atomic%, and the content of Al atoms is 0.1 to 5 atomic%, the content of Si atom is 0.1 to 5 atomic%, and the content of Co atom or Ca atom (the total amount when both are contained) is 0.1 to 13 atomic%. Fe, Ni, Al, Si, and C atoms present in a surface region of 100 ° or less at a depth of analysis of ferromagnetic powder by ESCA (X-ray photoelectron spectroscopy) of less than 100 °
The content ratio of o atoms and / or Ca atoms is F
e: Ni: Al: Si: (Co and / or Ca) = 10
0: (4 or less): (10 to 60): (10 to 70):
Those having a structure of (20 to 80) are preferable.

The shape of the ferromagnetic powder is such that the major axis diameter is 0.3.
0 μm or less, preferably 0.20 μm or less. According to such a ferromagnetic powder, the surface property of the coloring material layer is improved.

Examples of the hexagonal plate-like powder include hexagonal ferrites such as barium ferrite and strontium ferrite.
i, Co, Zn, In, Mn, Ge, Hb, etc.).
E trans on MAG, p. 18, 16 (198
Those described in 2) can be mentioned. Among these, as an example of the barium ferrite magnetic powder, an average particle size in which at least a part of Fe is replaced by Co and Zn (diagonal height of the plate surface of hexagonal ferrite) is 400.
And a plate ratio (a value obtained by dividing a diagonal length of a plate surface of hexagonal ferrite by a plate thickness) of 2.0 to 10.0 °.
It is. In addition, barium ferrite magnetic powder further contains Fe
May be substituted with a transition metal such as Ti, In, Mn, Cu, Ge, or Sn.

A method for producing a cubic magnetic powder is, for example, by melting oxides and carbonates of each atom necessary for forming a target barium ferrite together with a glass-forming substance such as boric acid. The glass melt is quenched to form a glass, and then the glass is heat-treated at a predetermined temperature to precipitate the desired barium ferrite crystal powder, and finally, the glass component is removed by a heat treatment. In addition to the method, there are a coprecipitation-calcination method, a hydrothermal synthesis method, a flux method, an alkoxide method, a plasma jet method and the like.

The content of the metal atom-containing particles contained in the coloring material layer is about 50 to 99% by weight, preferably 60 to 95% by weight of the coloring material layer forming component.

The binder resin can be used without any particular limitation as long as it can sufficiently retain a colorant capable of absorbing the wavelength light of the exposure light source and particles containing metal atoms. Polyurethane as the binder resin, polyester, and the vinyl chloride resins such as vinyl chloride copolymers representative and these resins _{-SO 3 M, -OSO 3 M,} -CO
Including a repeating unit having at least one polar group selected from OM and —PO (OM ₁ ) ₂ [M represents a hydrogen atom or an alkali metal atom, and M ₁ represents a hydrogen atom, an alkali metal atom or an alkyl group] It is preferable to use a resin into which such a polar group is introduced, so that the dispersibility of the magnetic powder can be improved. Incidentally, the content ratio of this polar group in each resin is about 0.1 to 8.0 mol%, preferably 0.2 to 6.0 mol%.

The binder resin may be used alone or in combination of two or more. When two or more binder resins are used in combination, for example, the ratio of polyurethane and / or polyester to vinyl chloride resin is 90:10. 10:90, preferably 70:30 to 30:70.

Examples of the vinyl chloride having a polar group include a resin having a hydroxyl group such as a vinyl chloride-vinyl alcohol copolymer, ClCH ₂ CH ₂ SO ₃ M, and ClCH ₂ CH ₂ OS.
O ₃ M, ClCH ₂ CO ₂ M, Cl _- CH ₂ P (= O) (O
It can be synthesized by an addition reaction with a compound having a polar group and a chlorine atom such as M ₁ ) ₂ (M and M ₁ are as described above). One example is shown below.

--CH ₂ C (OH) H-+ ClCH ₂ CH ₂
SO ₃ Na → —CH ₂ C (OCH ₂ CH ₂ SO ₃ Na) H—The polar group-containing vinyl chloride resin is an autoclave in which a predetermined amount of a reactive monomer having an unsaturated bond into which a repeating unit containing a polar group is introduced. Can be obtained by polymerization using a general radical polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, or a redox polymerization initiator, a cationic polymerization initiator, etc. Specific examples of the reactive monomer for introducing sulfonic acid or a salt thereof include unsaturated hydrocarbon sulfonic acids such as vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, and p-styrene sulfonic acid, and salts thereof. be able to.

When a carboxylic acid or a salt thereof is introduced, for example, (meth) acrylic acid or maleic acid is used, and when a phosphoric acid or a salt thereof is introduced, (meth) acryl-2-acid is used.
A phosphate may be used.

In order to further improve the thermal stability of the binder resin, it is preferable to introduce an epoxy group into the vinyl chloride copolymer. In this case, the content of the repeating unit having an epoxy group in the copolymer is 1 to 30 mol%.
And preferably 1 to 20 mol%, and glycidyl acrylate can be used as a monomer for introducing an epoxy group.

The polyester having a polar group can be synthesized by a dehydration condensation reaction between a polyol and a polybasic acid partially having a polar group. Examples of the polybasic acid having a polar group include 5-sulfoisophthalic acid, -Sulfoisophthalic acid, 4-sulfoisophthalic acid, 3-sulfophthalic acid, 5
-Dialkyl sulfoisophthalate, dialkyl 2-sulfoisophthalate, dialkyl 4-sulfoisophthalate,
Examples thereof include dialkyl 3-sulfophthalates and alkali metal salts thereof. Examples of the polyol include trimethylolpropane, hexanetriol, glycerin, trimethylolethane, neopentyl glycol, pentaerythritol, ethylene glycol, propylene glycol, and 1,3-butane. Examples thereof include diol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanedimethanol.

The polyurethane having a polar group can be synthesized by reacting a polyol with a polyisocyanate, and specifically, by reacting a polyol with a polybasic acid partially having a polar group as a polyol. It is synthesized by using the obtained polyester polyol as a raw material. Examples of the polyisocyanate include diphenylmethane-4,4'-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, and lysine isocyanate methyl. Esters and the like can be mentioned.

As another method for synthesizing a polyurethane having a polar group, a polyurethane having a hydroxyl group and ClCH ₂ CH ₂ SO ₃ M, ClCH ₂ having a polar group and a chlorine atom can be used.
_{CH 2 OSO 3 M, ClCH 2} C0 2 M, ClCH 2 P (=
An addition reaction with a compound such as O) (OM ₁ ) ₂ [M and M ₁ are as described above] is also effective.

Other binder resins include vinyl chloride resins such as vinyl chloride-vinyl acetate copolymer, polyolefin resins such as butadiene-acrylonitrile copolymer, polyvinyl acetal resins such as polyvinyl butyral, and celluloses such as nitrocellulose. Resin, styrene resin such as styrene-butadiene copolymer, acrylic resin such as polymethyl methacrylate, polyamide,
Although a phenol resin, an epoxy resin, a phenoxy resin and the like may be used in combination, when these are used in combination, the content is preferably 20% by weight or less of the total binder resin.

The content of the binder resin in the coloring material layer is about 1 to 50% by weight, preferably 5 to
40% by weight.

In the coloring material layer, a durability improving agent, a dispersing agent, an antistatic agent, a filler,
An additive such as a curing agent may be included.

Examples of the durability improver include polyisocyanate. 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; azo compounds having a carboxyl group and a sulfo group, and the like; examples of the antistatic agent include cationic surfactants and anions System surfactants, nonionic surfactants, polymer antistatic agents, conductive fine particles, etc.,
"Chemical products of 11290" Chemical Daily, 875-8
Compounds described on page 76 and the like can be mentioned. As the filler, carbon black, graphite, silica gel, 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-FeOO
H, SiC, CeO ₂ , BN, SiN, MoC, BC,
WC, titanium carbide, corundum, artificial diamond, feldspar, garnet, quartzite, acid clay, activated clay,
Examples include inorganic fillers such as tribori, diatomaceous earth, and dolomite, and organic fillers such as polyethylene resin particles, fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles, and melamine resin particles.

The inorganic / organic resin particles vary depending on the specific gravity, but are preferably added in an amount of 0.1 to 70% by weight. These may also serve as release agents.

The curing agent can be used without any particular limitation as long as it can cure the colorant layer. Examples thereof include polyisocyanate used when synthesizing the polyurethane in the binder resin described above. be able to. By adding a curing agent to cure the colorant layer,
In addition to increasing the durability of the formed image, it is possible to eliminate the background stain on the portion where ablation has occurred.

Further, since the durability to a solvent can be improved, the protective layer can be laminated without damaging the image forming layer even when an organic solvent is used when applying the protective layer. As a result, an image forming material having more excellent durability than the protective layer made of a water-soluble or water-dispersible resin can be prepared.

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

The thickness of the color material layer is about 0.05 to 5.0 μm, preferably 0.1 to 3.0 μm. or,
The color material layer may be composed of a single layer or a multilayer having different compositions. Is preferably contained more. Further, a colorant capable of absorbing light having a wavelength other than the wavelength of the exposure light source may be added to the layer farther from the support.

The coloring material layer is prepared by, for example, kneading a coloring material, a binder resin, and, if necessary, a durability improver, a dispersant, an antistatic agent, a filler, a filler, a curing agent, and a solvent, to prepare a coating material. The coating is then diluted, applied to a support and dried to form a coating.

Examples of the solvent include alcohols (ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve), aromatics (toluene, xylene, chlorobenzene, etc.), ketones (acetone, methyl ethyl ketone, etc.), and esters. Solvents (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, dioxane, etc.), halogen solvents (chloroform, dichlorobenzene, etc.), amide solvents (dimethylformamide, N
-Methylpyrrolidone, etc.). or,
For kneading and dispersing the components of the image forming layer, a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a cobol mill, a tron mill, a sand mill, a sand grinder, Sqeg
A vari attritor, high-speed impeller disperser, high-speed stone mill, high-speed impact mill, disper, high-speed mixer, homogenizer, ultrasonic disperser, open kneader, continuous kneader, or the like can be used.

The formation of the color material layer on the support is carried out, for example, by applying and drying with an extrusion-type extrusion coater. If necessary, the magnetic powder may be subjected to a calendering treatment in order to make the orientation thereof uniform or to make the surface properties of the image forming layer uniform. In particular, in order to obtain a high-resolution image, it is preferable to orient the magnetic powder because the cohesive force in the layer can be easily controlled.

Further, when a protective layer is provided on the color material layer, the coating and drying may be repeated for each layer, but the coating may be performed by multi-layer coating by a wet-on-wet method and dried. In that case, reverse roll, gravure roll, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, bar coater, transfer roll coater, kiss coater, cast coater or spray coater or the like can be applied by a combination with an extrusion coater. it can.

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

The effect of the present invention can be more remarkably exhibited by calendering the surface of the color material layer. The calendar treatment in the present invention means that after laminating a color material layer on a support, usually, a high smoothness nip roller having a diameter of 1 to 100 cm and a heatable roller facing the nip roller are heated and heated. This is a step of reducing the voids in the color material layer generated in the steps of applying and drying the color material layer coating liquid, and increasing the density of the color material layer itself. Conditions for the calendering treatment are as follows. In order to reduce the porosity of the color material layer, the linear pressure is usually 2 to 100.
It is preferable to apply a nip thickness of 5 kg / cm, preferably 5 to 50 kg / cm. As the heating temperature,
Usually, it is 40 to 200 ° C., preferably 50 to 120 ° C. However, since the optimal heating temperature varies depending on the transport speed,
Usually, it is set so that the maximum instantaneous temperature at which the color material layer heats up during the calendering process is about 30 to 100 ° C.

When the linear pressure and the heating temperature of the calendering treatment are lower than these ranges, the effect of the present invention is small. When the linear pressure and the heating temperature are high, defects such as deformation and cracking occur in the support of the image forming material and the colorant layer itself. It is not preferable.

The calendering treatment is preferably performed immediately after the coloring material layer is applied irrespective of the presence or absence of the curing treatment of the coloring material layer. However, if necessary, the calendering treatment may be performed after coating and laminating the protective layer.

The thickness of the protective layer is usually 0.03 to 1.0 μm
And preferably 0.05 to 0.5 μm. One embodiment of the image protective layer of the present invention mainly comprises a resin binder and a lubricant.

The binder resin can be used without any particular limitation as long as it can sufficiently retain the nonmetallic fine particles. Specifically, vinyl chloride resins such as polyurethane, polyester and vinyl chloride copolymer, vinyl chloride-
Vinyl chloride resins such as vinyl acetate copolymer, polyolefin resins such as butadiene-acrylonitrile copolymer, polyvinyl acetal resins such as polyvinyl butyral, cellulose resins such as nitrocellulose, and styrene such as styrene-butadiene copolymer. Resin, acrylic resin such as polymethyl methacrylate, polyamide, phenolic resin, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl acetal, acetal resin such as polyvinyl formal, and water-soluble resin 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 components for forming the image protective layer. It is preferable to add a curing agent such as polyisocyanate in order to increase the durability of the protective layer. As the 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 the 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 It is preferable to use

The protective layer of the present invention preferably contains additives (lubricants) such as wax, silicon compound and fluorine compound.

Specific compounds as wax include beeswax,
Solid waxes such as candelilla wax, paraffin wax, ester wax, montan wax, carnauba wax, amide wax, polyethylene wax, microcrystalline wax and the like.

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,
Radical reactive silicone oils such as higher fatty acid modified silicone oils, carnauba modified silicone oils, amide modified silicone oils, (meth) acrylic modified silicone oils, terminal reactive silicone oils such as silicon diol and silicon diamine, halogen atoms, alkoxy groups And an organically modified silicone oil modified with an ester group, an amide group, an imide group or the like.

Examples of the fluorine compound include polytetrafluoroethylene, tetrafluoroethylene copolymer (alkyl vinyl ether, ethylene, etc.), polyvinylidene fluoride, fluoroalkyl methacrylate,
Fluorinated resins such as fluorine rubber, perfluoropolyether oil, fluorine alcohol, fluorine carboxylic acid, perfluoroalkyl carboxylate, perfluoroalkyl quaternary ammonium salt, perfluoroalkyl betaine, perfluoroalkyl ethylene oxide (adduct) And low molecular weight fluorine compounds such as perfluoroalkyl oligomers. The individual amount of each of these additives is
It is preferably 0.1 to 30% by weight of the solid content in the overcoat layer (protective layer), more preferably 0.5 to 2%.
0% by weight. When multiple additions are made, the number is a multiple of this.

Next, the back coat layer of the present invention will be described.

The back coat layer is provided for the purpose of maintaining the antistatic property and the transportability and improving the heat resistance. As one means for improving heat resistance, the binder resin has a glass transition point of 75 ° C. or more, or has a glass transition point of 7 ° C.
A mixed system of a resin having a temperature of 5 ° C. or more and a polymer having a glass transition point of less than 75 ° C. On the other hand, another means for improving heat resistance is that the melting point of wax used as a lubricant for improving transportability is 80 ° C. or higher.

The binder resin is not particularly limited as long as it is a resin capable of dissolving or dispersing the antistatic agent. Specifically, polyester resin, polyvinyl chloride resin, polyvinyl butyral resin, polyacrylate resin, polyurethane resin, cellulose resin, aromatic polyamide resin, silicone resin, epoxy resin, alkyd resin, phenol resin, melamine resin, fluorine Resins, polyimide resins, acrylic resins, urethane-modified silicone resins, polyethylene resins, polypropylene resins, and the like.

As a lubricant, it is preferable to add wax, silicon compound, fluorine compound and the like. For these compounds, the aforementioned protective layer additives (lubricants)
And the same.

The total amount of the lubricant added is preferably from 0.1 to 30% by weight, more preferably from 0.5 to 15% by weight, of the solid content in the back coat layer.

The back coat layer contains an antistatic agent for imparting antistatic properties. Further, conductive fine particles may be used in combination.

Examples of the antistatic agent include cationic surfactants such as quaternary ammonium salts and polyamine derivatives; anionic surfactants such as alkyl phosphate; double-sided ionic surfactants such as betaine; and fatty acid esters. Non-ionic surfactants such as polysiloxane-based surfactants can be used. In addition, a water-soluble acrylic resin of amphoteric or cationic type can form a back coat layer alone without a binder.

The conductive fine particles need only have conductivity, for example, metal oxide fine particles which easily form nonstoichiometric compounds such as oxygen-deficient oxides, metal-rich oxides, metal-deficient oxides, and oxygen-rich oxides. Is mentioned. Among them, the most preferable compounds for the present invention are metal oxide fine particles which can employ various methods in production methods and the like. For example, crystalline metal oxide particles are common, for example, ZnO, TiO
₂ , SnO ₂ , Al ₂ O, In ₂ O ₃ , SiO ₂ , MgO, B
Examples include ₂ O, MoO ₃ , and composite oxides thereof. Of these, ZnO, TiO ₂ , Sn
O ₂ is preferable, and as a composite oxide, A
l, In, etc. For TiO ₂ , Nb, Ta, etc., Sn
For O ₂ Sb, Nb, it is preferably one of the different element comprises 0.01 to 30 mol%, such as halogen, is particularly include 0.1 to 10 mol% preferred. Further, the volume resistivity of these conductive fine particles is preferably 10 ⁷ Ω / cm or less, particularly preferably 10 ⁵ Ω / cm or less. It is preferable to include a compound having oxygen vacancies in the crystal and a small amount of a different kind of atom serving as a so-called donor for the metal oxide because conductivity is improved. Details of the production of such conductive fine particles are described in, for example, JP-A-56-143430.

As the binder of the conductive layer used for the conductive fine particles, proteins such as gelatin, derivative gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethylcellulose, hydroxyethylcellulose, diacetylcellulose and triacetylcellulose; agar, arginine Sugar derivatives such as sodium citrate and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives and partial hydrolysates thereof; Vinyl polymers such as acrylonitrile and polyacrylates and copolymers thereof; natural products such as rosin and shellac and derivatives thereof, and many other synthetic resins are used. Emulsions such as styrene-butadiene copolymer, polyacrylic acid, polyacrylate and derivatives thereof, polyvinyl acetate, vinyl acetate-acrylate copolymer, polyolefin, and olefin-vinyl acetate copolymer are also used. be able to. In addition, organic semiconductors such as carbonate-based, polyester-based, urethane-based, epoxy-based resins, polyvinyl chloride, polyvinylidene chloride, and polypyrrole can also be used. These binders can be used as a mixture of two or more kinds.

From the viewpoints of ease of handling during production and product performance, among these binders, particularly, polyacrylic acid copolymers, polyacrylamides, polyacrylonitriles, polyacrylic esters, polycarbonates, polyesters, polyvinyl chlorides and the like. Polyvinylidene chloride is preferred.

In order to improve the adhesion between the conductive layer and the support, a compound capable of swelling the support can be contained in the conductive layer. Specific compounds include, for example, resorcinol, chlorresorcinol, methylresorcinol,
o-Cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, foam water chloral, and the like. However, resorcin and p-chlorophenol are particularly preferred.

The ratio of the conductive fine particles is 10% by volume content.
To 70%, more preferably 15 to 50%, and the amount used is 0.05 to 5.0 g / m ² , preferably 0.1 to 50 g / m ² .
2.0 g / m ² . The compound that swells the support is 0.01 to 5.0 g / m ² , preferably 0.05 to 1.0 g / m ² .
0 g / m ² .

The antistatic agent and the conductive fine particles are used by being dissolved or dispersed in an organic solvent or an aqueous solution in which the binder is dissolved.

In applying the back coat layer, a solvent is appropriately selected to prepare a coating solution. Selection of a solvent can be easily performed by those skilled in the art. As a coating method, it is possible to select and adopt any method from known methods such as a normal coating method, for example, a blade coater, a roll coater, a bar coater, a curtain coater, a gravure coater, an extrusion lamination method, and a bonding method. it can.
Further, at the time of coating, known coating aids such as saponin and dodecylbenzenesulfonic acid, and hardeners, coloring agents, ultraviolet absorbers, heat ray cutting agents, and the like can be appropriately added to the coating solution as needed.

In order to improve the adhesion between the support and the back coat layer, an undercoat layer may be provided between them.

The surface resistivity of the back coat layer can be adjusted by adjusting the volume content of the antistatic agent and the conductive fine particles in the back coat layer and / or by adjusting the thickness of the back coat layer. By the above adjustment, the surface specific resistance value is preferably set to 10 ¹¹ Ω / cm ² or less.

However, in order to have sufficient strength as a back coat layer, the amount of the binder resin should be 5
Preferably it does not fall below the weight percentage. In the case of the antistatic agent, the proportion of the antistatic agent is 0.5 to 30% by weight, more preferably 1 to 10% by weight, and the amount of the antistatic agent is 0.001%.
１1 g / m ² , preferably 0.002 to 0.05 g / m ²
In the case of conductive fine particles, the volume content is 10 to 70
%, More preferably 15 to 50%, the amount used 0.01-5 g / m ^2, preferably 0.1-2 g / m ^2.

In addition, the antistatic layer may optionally contain additives for improving coating properties, such as a surfactant.

The back coat layer of the present invention is preferably provided so that the smoother value is 7 to 200 mmHg. In order to obtain this smoother value, a means for roughening the surface of the back coat layer is optimal. The smoother value was measured at 23 ° C. using a vacuum-type air macrometer (manufactured by Toei Electric Industry Co., Ltd .: Smooster SM-6B).
Under the condition of 55% RH, the amount of air flowing in according to the roughness of the surface to be measured adsorbed on the measuring head is measured as a change in pressure mmHg. The smoother value is correlated with the surface matte degree, and the higher the pressure value, the higher the matte degree.

As means for roughening, a matting material is added to the coating liquid for the back coat layer, the back coat layer is embossed, the back coat layer is provided on an uneven support, and a roughening roll is used. Although a method of forming irregularities on the surface of the back coat layer may be mentioned, any method can be applied as long as the surface of the back coat layer can be roughened. In particular, a method in which a mat material is added to the coating liquid for the back coat layer is the simplest, effective, and preferable method. Organic or inorganic fine particles can be used as the mat material. Organic mat materials include polymethyl acrylate, polystyrene, polyethylene, polypropylene, fluororesin, guanamine resin, acrylic resin, styrene-acryl copolymer resin, silicone resin,
Resin particles such as melamine resin and epoxy resin, fine particles of other radical polymerizable polymers, fine particles of condensed polymers such as polyester and polycarbonate, and the like.

Examples of the inorganic matting material include metal oxides (silica, zinc oxide, alumina, titanium oxide, etc.), silicates (calcium silicate, etc.), sulfates (calcium sulfate, barium sulfate, etc.), carbonates (calcium carbonate, etc.). Etc.).

The degree of roughening of the back coat layer is determined by the smoother value. If the smoother value is too small, problems such as poor transportability in the image forming apparatus and time required for close contact with the PS plate when printing the formed image on the PS plate occur. On the other hand, if the value of the smoother value is too large (= the surface of the backcoat layer has large irregularities), when exposure is performed from the backcoat layer side,
Light scattering occurs, causing problems such as a decrease in sensitivity and a decrease in image quality.

When a mat material is used, the particle size and content of the mat material are selected so as not to affect the image due to scattering of light when exposed imagewise to the smoother value. The content is preferably 1 to 10 μm, and the content is preferably 0.01 to 1 g / m ² .

In addition, the back coat layer can also contain additives for improving coating properties, such as a surfactant, if necessary.

In order to increase the bonding strength between the support and the back coat layer within a range not to impair the effects of the present invention, an adhesive may be contained in the back coat layer, the back coat layer may be cured, Alternatively, an intermediate layer or the like may be provided.

The back coat layer is provided on the image forming sheet and / or the sheet to be transferred, but is preferably provided on the image forming sheet in the present invention.

<Transfer-Received Sheet> The transfer-receiving sheet has an image forming layer (color material layer (and protective layer)) in which the bonding strength between the support and the color material layer in the irradiated area has been reduced by exposure to high-density energy light.
This is a member that can transfer the image forming layer of the irradiated part by separating the part from the support that holds the color material layer and that can receive the part.

In the image forming method of the present invention described below,
The transfer sheet provided to receive an image after peeling after image exposure can be used as a transfer sheet support using a resin film used as a support such as the above image forming material support. A film provided with an image receiving layer capable of receiving the image forming layer of the high-density energy light irradiation portion on a film can be used.

Examples of the support include synthetic paper (such as synthetic paper containing polypropylene as a main component). Specifically, each grade of Peachcoat manufactured by Oji Yuka Kabushiki Kaisha: trade name Yupo or Nisshinbo Co., Ltd., or Dianal W-900E manufactured by Diafoil Hoechst Co., Ltd. can be preferably used.

The substrate made of a resin is preferably stretched into a sheet or film and heat-set, from the viewpoint of dimensional stability, and may be appropriately selected depending on the use, even if it has no microvoids or has microvoids. can do. Specifically, manufactured by Diafoil Hoechst: W
-400 and T-100E are preferred.

The base paper used as the support of the transfer object is preferably pulp paper made from natural pulp, synthetic pulp, or a mixture thereof, and among them, natural pulp paper mainly containing wood pulp is preferable. . The paper is formed using a fourdrinier paper machine or the like, and is preferably subjected to a calendering process using a machine calender, a super calender, a heat calender or the like after the paper making for the purpose of improving smoothness. A base paper coated with a pigment-containing resin layer for improving smoothness can also be suitably used. Specific base papers include high quality paper, art paper, coated paper, matte paper, impregnated paper, paperboard, and the like.

The paper is preferably provided with a Bekk smoothness of 50 seconds or more in order to impart smoothness when a laminating layer of polypropylene and polyolefin containing white fine particles described later is provided. As described above, it is preferable to have smoothness of 200 seconds or more. The thickness of the paper is not particularly limited, but is preferably 30 to 800 μm,
50 to 500 μm is more preferable.

In the base paper, if necessary, additives such as a sizing agent, a fixing agent, a paper strength enhancer, a filler, an antistatic agent, a dye, a pigment, a fluorescent whitening agent, an antioxidant and a lubricant are used. May be included.

As the base material, a transparent original such as OHP,
When transparency is required, such as in sealing applications to be adhered to glass or the like, a material having high transparency is preferable, and in the case of a reflection image, a base material is used to enhance the sharpness of the formed image. White pigments such as titanium oxide, zinc oxide, silica, barium sulfate, magnesium carbonate, calcium carbonate, talc, clay and the like may be added to the layer.

The thickness of the substrate is usually from 20 to 1000 μm, preferably from 50 to 500 μm, and is appropriately selected from such a range. Since the transfer receiving body becomes unnecessary after image formation, it is preferable that its thickness is as thin as possible from the viewpoint of reducing waste materials. However, if the thickness is too small, there is a fear that the transfer receiving body may be broken when the transfer receiving body is peeled off from the image forming layer, and there is a concern that the transferability of the transfer receiving body after peeling may be difficult, so that the support The thickness is usually 6-10
It is about 0 μm, preferably 12 to 50 μm.

The receiving layer used in the image forming material of the present invention mainly comprises a thermoplastic resin binder. As the resin binder to be used, urethane resins, acrylic resins, and styrene copolymer elastomers are preferably used. As a urethane resin, a urethane bond (-N
A resin having HCOO-), specifically, Nipporan, a polyurethane resin for adhesive manufactured by Nippon Polyurethane Industry Co., Ltd.

Examples of the acrylic resin include ethylene-ethyl acrylate copolymer resin (EEA), ethylene-acrylic acid copolymer resin (EAA), and other modified acrylic resins. Specifically, EV manufactured by DuPont-Mitsui Polychemicals Ltd .:
AFLEX-EEA and Nipol LX series manufactured by Zeon Corporation.

Examples of styrene copolymer elastomers include SBS in which polystyrene block (S) and polybutadiene (B), polyisoprene (I), polyethylene / butylene (EB), and polyethylene / propylene (EP) blocks are copolymerized in the molecule. SIS, SEBS, SEPS and the like can be preferably used. Specific examples include Califlex TR, Clayton D, Clayton G, manufactured by Shell Japan Co., Ltd. and Septon, Hibler, manufactured by Kuraray Co., Ltd. and Tuftec H and M series manufactured by Asahi Kasei Corporation. In addition, other resins can be mixed in an arbitrary ratio as long as the effects of the present invention are not impaired.

An inorganic or organic filler can be added to the image receiving layer as needed. Examples of the inorganic fine particles include metal oxides such as silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, and aluminum borate; calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, and boron nitride. Metal salts such as kaolin, clay, talc, zinc white, lead white, ziglite,
Quartz, diatomaceous earth, perlite, bentonite, mica, synthetic mica and the like can be mentioned.

Examples of the organic fine particles include melamine resin particles, guanamine resin particles, styrene-acryl copolymer resin particles, silicone resin particles, and fluorine resin particles. The thickness of the image receiving layer is usually 0.01 to 10 μm.
m, preferably 0.1 to 5 μm.

The back coat layer of the transfer sheet is formed using the same material as the back coat layer of the image forming sheet. However, when laser exposure is performed from the back coat layer side of the image forming sheet, the amount of the mat material in the back coat layer of the transfer sheet is not limited as much as the amount of the mat material in the back coat layer of the image forming sheet. The amount of mat material can be increased to improve.

Referring to the drawings, FIG. 1A is a schematic view of one preferred embodiment of the image forming material of the present invention.
The support has a color material layer 2, preferably a protective layer 4, on the support 1, and a back coat layer 3 on the surface of the support opposite to the color material layer.

FIG. 1B is a schematic view of another preferred embodiment of the image forming material of the present invention. The image receiving layer 10 of the transfer sheet is adjacent to the protective layer 8 of the image forming sheet. This is an integrated image forming material having a back coat layer 11 on the surface of the sheet support opposite to the image receiving layer side.

<Image Forming Method> In a preferred image forming method of the present invention, an image forming material having a color material layer and a protective layer on a support in this order is exposed to high-density energy light to form After reducing the bonding force with the material layer (ablation), an image is formed by removing the color material layer and the protective layer in the irradiated area.

In the present invention, images can be formed by two methods based on the above-described constitution of the image forming material. Hereinafter, each image forming method will be described in detail.

-Image Forming Method 1- The image forming material has a color material layer and a protective layer on a support in this order, and the bonding strength between the support and the color material layer in the irradiated area by exposure to high-density energy light. Then, an image is formed using a means capable of removing only an image forming layer portion (hereinafter referred to as an ablation portion) having a reduced bonding force with the support. As a specific means, there are a method of peeling after adhesion using a pressure-sensitive adhesive sheet, a method of sucking and removing an ablation part, a method of shaving off with a brush, and a method of blowing off with an air brush.

The image exposure is performed by using an electromagnetic wave whose energy application area can be narrowed down, in particular, a wavelength of 1 nm in order to obtain a high resolution.
Ultraviolet rays, visible rays, and infrared rays of up to 1 mm are preferable. Examples of light sources to which such light energy can be applied include lasers, light emitting diodes, xenon flash lamps, halogen lamps, carbon arc lamps, metal halide lamps, tungsten lamps, and quartz mercury. Lamps, high-pressure mercury lamps, and the like. The energy applied at this time depends on the type of the image forming material, the exposure distance,
By adjusting the time and intensity, it can be selected as appropriate.

In the case of batch exposure of energy, a mask material in which a negative pattern of a desired exposure image is formed of a light-shielding material may be overlaid and exposed.

When an array-type light source such as a light-emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp, or a tungsten lamp is subjected to exposure control using an optical shutter material such as a liquid crystal or PLZT, an image signal is used. It is possible to carry out the corresponding digital exposure. In this case, direct writing can be performed without using a mask material. However, this method requires a new optical shutter material in addition to the light source. Therefore, in the case of digital exposure, it is preferable to use a laser as the light source.

When a laser beam is used as a light source,
It is possible to form a latent image by scanning light according to image data by squeezing light into a beam, and furthermore, by using a laser as a light source, it is easy to narrow the exposure area to a very small size, and it is possible to form a high-resolution image Formation is possible.

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

Regarding the exposure direction of the high-density light energy, the exposure can be performed from the support side or the image forming layer side of the image forming layer.

Examples of the method of peeling the transfer object include a peeling plate, a method of fixing a peeling angle by a peeling roll, and a hand peeling method of peeling off the transfer sheet and the image forming material without fixing by hand. Various peeling methods can be used if they do not affect the formation. For example, image formation is performed by exposing the image forming layer and the object to be transferred to each other with a non-tacky or non-adhesive object at normal temperature after exposure, and then thermocompression-bonding with a heat roll or the like, and peeling the object to be transferred. can do.

Although the above description has been made with reference to an image forming material in which only an image forming layer is laminated on a support, when an intermediate layer is laminated between the support and the image forming layer, ablation is performed. The position may be between the intermediate layer and the image forming layer, between the support and the intermediate layer, or in some cases, the intermediate layer may be partially destroyed by heat.

-Image Forming Method 2- A second method uses an image forming material in which a sheet to be transferred is previously laminated on the above-described image protective layer, and the image forming material is supported by exposure to high-density energy light. After the bonding force between the body and the image forming layer is reduced, the image forming layer of the irradiated portion is transferred to the transfer sheet by separating the transfer sheet and the support.

As a method of previously laminating the transfer-receiving sheet, a resin having tackiness is applied on a transfer-receiving-substrate support at room temperature or by heating at the above-described extrusion lamination, or dispersed or dissolved in water or a solvent, followed by coating and drying. Obtained by: As a method of laminating the transfer-receiving member on the image protective layer, the transfer can be performed by applying pressure to a pair of opposing bonding rollers so as to bring them into close contact with each other. When the transfer object has adhesiveness by heating, it is preferable to secure adhesion by heating immediately before or during the laminating roller, or after laminating.

The peeling force required for peeling the image protective layer of the thus formed image forming material and the transfer-receiving member is determined according to JIS.
It is preferably 5 to 50 gf / cm in the 180 degree peeling method of C 2107 (JIS Z 0237).

Also, in this method, the image forming method 1 is used.
Similarly to the above, the exposure direction of the light energy is preferably exposed from the side of the support, and further, the destruction of the color material layer in the image exposed portion does not occur, so that only the adhesive force between the support and the color material layer is reduced or eliminated. Image exposure is preferred because the image exposed portion can be uniformly pulled out to the transfer sheet side.

The thickness of the sheet to be transferred is preferably 5 to 300 μm, which is common to the above two image methods.
Further, the thickness is preferably 10 to 150 μm.

The above image forming method will be specifically described with reference to the drawings.

FIGS. 2A to 3D are schematic views of an example of an image forming method using the image forming material A. The high-density energy light 12 is irradiated from the side of the back coat layer 3 (a), the bonding strength between the support 1 and the image forming layer 2 in the irradiated part is reduced (b), and the image forming layer 2 and the transferred object face each other. Then, after thermocompression bonding with a heat roll (c), the image receiving layer is transferred to the image receiving layer by separating the image receiving layer from the support 1 to form an image (d).

FIGS. 4E to 5H are schematic views of an example of an image forming method using the image forming material B. Irradiation is performed with the high-density energy light 12 from the back coat layer 7 side of the image forming sheet of the image forming material integrated in advance (e) to reduce the bonding force between the support 5 and the image forming layer 6 in the irradiated part ( f), the image-receiving sheet is separated from the image-forming sheet (g), whereby the image-forming layer 6 of the irradiation section is transferred to the transfer-receiving member, thereby forming an image (h).

[0143]

EXAMPLES The present invention will be described in detail below with reference to examples, but embodiments of the present invention are not limited to these examples. In Examples, "parts" means "parts by weight as active ingredient" unless otherwise specified.

Example 1 (Preparation of Image Forming Material) The image forming materials according to the present invention and the comparative examples are shown in the following image forming sheets (support, color material layer,
(Consisting of a protective layer and a back coat layer) and a sheet to be transferred.

<< Image Forming Sheet >><Support> A transparent polyethylene terephthalate (PET) film (T-100, manufactured by Diafoil Hoechst Co., Ltd.) having a 100 μm-thick color material layer laminated surface subjected to corona discharge treatment was used.

<Coloring Material Layer> The following composition was kneaded and dispersed using an open kneader to prepare a coating material for a coloring material layer containing a magnetic powder composed of a metal, which was applied on a support by extrusion coating. The magnetic field orientation treatment was performed while the coating film was not dried, followed by drying and then surface treatment with a calender under the following conditions, followed by heat treatment at 60 ° C. for 72 hours to complete the curing reaction. A color material layer having a thickness of 0.9 μm was formed.

Colorant layer coating liquid Fe-Al-based ferromagnetic metal powder (colorant and metal-containing powder) colorant (Fe: Al atomic ratio = 100: 4 (overall), 50:50 (surface), 100 parts Vinyl chloride resin containing potassium sulfonate group 10 parts (manufactured by Zeon Corporation: MR-110) Polyurethane resin containing sodium sulfonate group 10 parts (Toyobo Co., Ltd .: UR-8700) α-Alumina (average particle diameter 0.15 μm) 8 parts Stearic acid 1 part Polyisocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd .: Coronate L) 5 parts Cyclohexanone 100 parts Methyl ethyl ketone 100 parts Toluene 100 parts (calender treatment) Metal having a diameter of 300 mm A calender roll in which a 3 mm-thick polyimide resin is wound around the outer circumference of the roll, and the diameter facing the calender roll Between metal rolls heated to 80 ° C. of 00mm were heat and pressure treatment at 10 m / min while applying a line pressure of 10 kg / cm.

<Protective Layer> A composition comprising the following resin binder and fine particles was laminated on the color material layer by wire bar coating so as to have a thickness of 0.25 μm.
Heat cured at 60 ° C. for 72 hours.

Protective layer composition Phenoxy resin (PKHH, manufactured by Union Carbide) 2.23 parts Polyisocyanate compound (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.6 part Polyethylene wax (manufactured by Koyo Chemical Co., Ltd .: Microflat) CE-155) 0.11 part Silicone resin fine particles (Silohobic 200 manufactured by Fuji Silysia Chemical Ltd.) 0.06 part Toluene 58.2 parts Cyclohexanone 38.8 parts <Back coat layer> On the opposite surface, a back coat layer having the following composition having a thickness of 0.5 μm
Coated and dried so that

Backcoat layer composition Binder (described in Table 1) 4.65 parts Antistatic agent (manufactured by Kao Corporation: Electrostripper QN) 0.15 part PMMA filler (manufactured by Soken Chemical Company: MX-150) 0.1 part Silicon resin (manufactured by Shin-Etsu Chemical Co., Ltd .: X-24-8300) 0.05 parts Wax (manufactured by Gifu Shellac Manufacturing Co., Ltd .: High Dispers 4055) 0.05 parts Methyl ethyl ketone 76 parts Cyclohexanone 19 parts << Transferred sheet >> 25 μm thick transparent PET An image receiving layer having the following composition was applied to a film (T-100E, manufactured by Diafoil Hoechst) so as to have a thickness of 1.2 μm.
After drying, a transfer-receiving sheet was obtained.

Image receiving layer composition Polyurethane resin (Nippon Polyurethane Industry Co., Ltd .: Nipporan 3109) 5.88 parts Silicone resin fine particles (Toshiba Silicone Co., Ltd .: Tospearl 120) 0.12 parts Toluene 45 parts Methyl ethyl ketone 38 parts Cyclohexanone 11 parts

[0152]

[Table 1]

(Image formation) Using a semiconductor laser (LT090MD, manufactured by Sharp Corporation) with a dominant wavelength of 830 nm, the surface of the color material layer is focused, and the image is exposed by scanning and exposing from the support side of the color material layer. After reducing the bonding force between the support and the colorant layer in the laser light irradiation section, the protective layer surface of the image forming sheet and the image receiving layer surface of the transfer sheet face each other, and a pressure roller (conveyance speed 30 mm / sec, pressure 3. 0kg /
cm), and an image was formed by peeling off the transfer-receiving sheet.

For each sample, the sensitivity (energy required for exposure), heat resistance, surface resistivity,
The coefficient of kinetic friction and the degree of mat (smooster value) were measured.

Table 2 shows the results.

<< Evaluation Method >> Sensitivity (energy amount required for exposure) An image forming material which is subjected to solid scanning exposure so as to form an image of 0.5 mm × 0.5 mm with a beam diameter of 10 μm to form an image. Average exposure on the surface (E ₁ : mJ / c unit)
m ² ) was evaluated on a four-point scale.

…: E ≦ 250…: 250 <E ≦ 400 Δ: 400 <E ≦ 600 ×: 600 <E • Heat resistance Diameter 5 cm (rubber hardness 85) heated to a surface temperature of 75 ° C.
Using a heat roller, 2 at a pressure of 150kg / cm ²
The surface of the back coat layer facing the heat roller by applying heat for 2 seconds was observed for erosion.

○: No change in surface △: Surface turbidity ×: Transfer of back coat layer to heat roll ・ Surface specific resistance The surface specific resistance of the back coat layer is 23 ° C./55% RH atmosphere, Teraohm manufactured by Kawaguchi Electric Co., Ltd. It measured using the meter VE-30.

Dynamic friction coefficient The dynamic friction coefficient of the back coat layer was set at 23 ° C. and 55% RH under a load of 1 using Haydon's Tribokia-14D.
The measurement was performed using a 00 g chrome sphere as a reference plane.

Matting degree (smooster value) The smoother value of the surface of the back coat layer was 23 ° C. and 55%
Under RH atmosphere, Smoother SM-6 manufactured by Toei Electric Industry Co., Ltd.
B was measured. With a vacuum type air macrometer,
The amount of air flowing in according to the roughness of the surface to be measured adsorbed on the measuring head was measured as a change in pressure (mmHg).

[0161]

[Table 2]

Example 2 (Preparation of Image Forming Material) The image forming materials of the present invention and the comparative example were prepared by using the following image forming sheet and the same transfer sheet as in Example 1.

<< Image Forming Sheet >> The same materials as in Example 1 were used for the support, the color material layer and the protective layer.

<Backcoat layer> On the surface opposite to the surface of the support having the color material layer, a backcoat layer having the following composition was applied to a thickness of 0.5 µm and dried.

Backcoat layer composition Polyester resin (manufactured by Toyobo Co., Ltd .: Byron 200) 4.65 parts Antistatic agent (supra: Electrostripper QN) 0.15 parts PMMA filler (supra: MX-150) 0.1 Part Silicon resin (described above: X-24-8300) 0.05 part Wax (described in Table 3) 0.05 part Methyl ethyl keto 76 parts Cyclohexanone 19 parts

[0166]

[Table 3]

Images were formed on Samples 8 to 12 by the same image forming method as in Example 1.

According to the same evaluation method as in Example 1, sensitivity, heat resistance,
Table 4 shows the results of the surface resistivity, the coefficient of kinetic friction, and the degree of mat (smoother value).

[0169]

[Table 4]

Example 3 (Preparation of Image Forming Material) Image forming materials of the present invention and comparative examples were prepared using the following image forming sheet and transfer sheet.

<< Image Forming Sheet >> The same materials as in Example 1 were used for the support and the colorant layer.

<Protective Layer> A composition comprising the following resin binder and fine particles was laminated on the color material layer by wire bar coating to a thickness of 0.25 μm.
Heat cured at 0 ° C. for 72 hours.

Protective layer composition Phenoxy resin (supra: PKHH) 2.23 parts Polyisocyanate compound (previous: Coronate HX) 0.48 parts Polyisocyanate compound (Nippon Polyurethane Industry Co., Ltd .: Coronate 3041) 12 parts Polyethylene wax (supra: Microflat CE-155) 0.11 parts Silicone resin fine particles (supra: Silo Hovic 200) 0.06 parts Toluene 58.2 parts Cyclohexanone 38.8 parts <Backcoat layer> On the surface opposite to the surface of the support having the material layer, a backcoat layer having the following composition having a thickness of 0.5 μm
Coated and dried so that

Back coat layer composition Binder (described in Table 5) 4.65 parts Antistatic agent (supra: Electrostripper QN) 0.15 parts PMMA filler (supra: MX-150) 0.1 parts Lubricant 1; Silicone resin (described in Table 5) 0.05 part Lubricant 2; wax (described in Table 5) 0.05 part Methyl ethyl ketone 76 parts Cyclohexanone 19 parts << Transferred sheet >> Transparent PET film having a thickness of 25 μm (described above: T-100E) An image receiving layer having the following composition was applied and dried to a thickness of 1.2 μm to obtain a transfer-receiving sheet.

Image receiving layer composition Polyurethane resin (supra: Nipporan 3109) 5.88 parts Silicone resin fine particles (supra: Tospearl 120) 0.12 parts Toluene 45 parts Methyl ethyl ketone 38 parts Cyclohexanone 11 parts <Backcoat layer> A back coat layer having the following composition having a thickness of 0.5
It was applied and dried to a thickness of μm.

Backcoat layer composition Binder (described in Table 6) 4.25 to 4.65 parts Antistatic agent (described above: Electrostripper QN) 0.15 part PMMA filler (described in Table 6) (described above: MX-) 150) 0.1 to 0.5 part Lubricant 1; silicone resin (described in Table 6) 0.05 part Lubricant 2; wax (described in Table 6) 0.05 part Methyl ethyl ketone 76 parts Cyclohexanone 19 parts

[0177]

[Table 5]

[0178]

[Table 6]

(Image formation) The protective layer surface of the image forming sheet and the image receiving layer surface of the transfer-receiving sheet are made to face each other, and they are bonded together by a pressure roller (transport speed: 30 mm / sec, pressure: 3.0 kg / cm). It was a body sample.

Semiconductor laser (LT090 manufactured by Sharp Corporation)
(MD, dominant wavelength 830 nm), focus on the surface of the color material layer, perform image exposure by scanning and exposing from the support side of the color material layer, and imagewise combine the support and the color material layer in the laser light irradiation part. Then, the image forming layer (color material layer and protective layer) was peeled off from the transfer-receiving sheet to form an image.

Table 7 shows the results of sensitivity, heat resistance, surface resistivity, coefficient of kinetic friction, and matte degree (Smooster value). The evaluation was performed in the same manner as in Example 1.

[0182]

[Table 7]

[0183]

According to the present invention, an image forming material having excellent sensitivity, heat resistance, surface resistivity, dynamic friction coefficient, and matte degree can be obtained, and high sensitivity and image quality can be obtained by using the image forming material. Excellent image formation is possible.

[Brief description of the drawings]

FIG. 1 is a schematic view of one preferred embodiment of the image forming material of the present invention, wherein A shows a separate type and B shows an integral type image forming material.

FIG. 2 is a process chart (a, b) for forming an image using the image forming material A of the present invention.

FIG. 3 is a process chart (c, d) for forming an image using the image forming material A of the present invention.

FIG. 4 is a process chart (e, f) for forming an image using the image forming material B of the present invention.

FIG. 5 is a process chart (g, h) for forming an image using the image forming material B of the present invention.

DESCRIPTION OF SYMBOLS 1,5 Support 2,6 Image forming layer (= color material layer) 3,7 Back coat layer of image forming sheet 4,8 Protective layer 9 Transfer receiving sheet support 10 Image receiving layer 11 Transfer receiving sheet Back coat layer 12 High density energy light (laser light)

Claims (22)

[Claims] 1. A support having at least one image forming layer on a support, wherein at least one of the image forming layers has a metal powder coloring material capable of absorbing wavelength light of an exposure light source dispersed in a resin binder, And an image forming material that undergoes ablation by exposure to high-density energy light, characterized in that it has a back coat layer in which the glass transition point of the binder is 75 ° C. or higher on the surface opposite to the support surface having the image forming layer. Image forming material. 2. A support having at least one image forming layer on a support, wherein at least one of the image forming layers has a metal powder colorant capable of absorbing wavelength light of an exposure light source dispersed in a resin binder, In an image forming material that undergoes ablation by exposure to high-density energy light, a polymer having a glass transition point of a binder of 75 ° C. or higher and a glass transition point of less than 75 ° C. on a surface opposite to the support surface having the image forming layer. An image forming material having a back coat layer which is a mixed system of polymers. 3. The image forming material according to claim 1, wherein the binder of the back coat layer is a polyester resin. 4. The image forming material according to claim 1, wherein the back coat layer contains at least one kind of lubricant. 5. The image forming material according to claim 4, wherein one of the lubricants in the back coat layer is a wax. 6. The image forming material according to claim 5, wherein the melting point of the wax is 80 ° C. or higher. 7. The image forming material according to claim 1, wherein the back coat layer contains an antistatic agent. 8. The image forming material according to claim 1, wherein the back coat layer contains a filler. 9. The back coat layer has a surface resistivity of 10 ^11.
The image forming material according to any one of claims 1 to 8, wherein the value is Ω / m ² or less. 10. The smooth coat value of the back coat layer is 7
10 to 200 mmHg.
The image forming material according to any one of the above. 11. The image forming material according to claim 1, wherein the image forming material is exposed to high-density energy light to reduce the bonding force between the support of the irradiating section and the image forming layer. An image forming method, wherein an image is formed by removing a forming layer. 12. A support having at least one image forming layer on a support, wherein at least one of the image forming layers has a metal powder coloring material capable of absorbing wavelength light of an exposure light source dispersed in a resin binder, And an image forming material formed by facing an image forming layer surface of an image forming sheet which causes ablation by exposure to high-density energy light and an image receiving layer surface of a transfer receiving sheet having an image receiving layer. An image forming material comprising a back coat layer on a surface opposite to a support having a formation layer and on a surface of the transfer-receiving sheet opposite to the support having the image receiving layer. 13. The image forming material according to claim 12, wherein the binder of at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet has a glass transition point of 75 ° C. or higher. 14. The binder for at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet is a mixed system of a polymer having a glass transition point of 75 ° C. or lower and a polymer having a glass transition point of 75 ° C. or higher. The image forming material according to claim 12, wherein: 15. The image forming material according to claim 12, wherein at least one of the binder of the back coat layer of the image forming sheet and the back coat layer of the sheet to be transferred is a polyester resin. 16. The image forming material according to claim 12, wherein at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet contains an antistatic agent. . 17. The image forming apparatus according to claim 12, wherein at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet contains at least one kind of lubricant. Image forming materials. 18. The image forming material according to claim 17, wherein one of the lubricants is wax. 19. The image forming material according to claim 18, wherein the melting point of the wax is 80 ° C. or higher. 20. The image forming material according to claim 12, wherein at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet contains a filler. 21. The smooth coater according to claim 12, wherein at least one of the back coat layer of the image forming sheet and the back coat layer of the transfer sheet has a smoother value of 7 to 200 mmHg. Image forming material. 22. The image forming material according to claim 12, wherein the image forming material is exposed to high-density energy light to reduce the bonding force between the support of the irradiated portion and the image forming layer. An image forming method, wherein an image is formed by removing a forming layer.