JP2006056139A - Ink sheet and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink sheet which is free from deterioration of sensitivity even through a long-time storage and exerts no adverse effect on natural environment and a human body, of which the dot gain value does not lower even at a low temperature/low humidity and which is also excellent in the reproducibility of a fine line, and a multicolor image forming method using the ink sheets in a plurality. <P>SOLUTION: An image receiving sheet having at least an image receiving layer on a substrate and the ink sheets in a plurality each having at least a photothermal conversion layer and an ink layer on a substrate are used, and the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to and laid on each other. A laser light is radiated from the ink sheet side and the laser light irradiated area of the ink layer is transferred onto the image receiving layer of the image receiving sheet, so as to record an image. In an image forming material having this constitution, the ink layer of the ink sheet contains at least one surfactant among those expressed by general formula (1) Rf<SB>1</SB>-OR<SB>1</SB>, general formula (2) Rf<SB>1</SB>-O-L-Rf<SB>1</SB>, general formula (3), general formula (4) and general formulas (5)-(7). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an image forming material (ink sheet and image receiving sheet) for thermal transfer recording and an image forming method using the image forming material.

  In the production of a thermal transfer image forming material using an infrared laser beam, it is usually necessary to laminate layers having various functions, and when the second and subsequent layers are laminated (such as the first layer) It is important to select materials, solvents, and production methods that take into account the effects on the lower layer.

  When forming a thermal transfer image on printing paper using laser light, an ink layer of an ink sheet having at least a photothermal conversion layer and an ink layer on a support, and an image receiving layer of an image receiving sheet having an image receiving layer on the support; The laser beam irradiation area of the ink layer is thermally transferred onto the image receiving layer of the image receiving sheet, and the image receiving sheet is further transferred to the final recording medium (printing paper). Although an image is obtained, the close contact between the ink sheet and the image receiving sheet is extremely important. In particular, when the recorded image has a high definition of 2,000 dpi (described above) or more, the close contact between both becomes increasingly important.

  One factor that greatly affects the adhesion is the smoothness of the ink sheet surface. Conventionally, various fluorine-based surfactants have been used in order to maintain the smoothness and coating properties of the ink layer (see, for example, Patent Document 1). However, there is a drawback in that the sensitivity decreases when the ink sheet is stored for a long period of time. there were. There are also surfactants that decompose during long-term storage and produce substances that may adversely affect the natural environment or the human body, and their replacement is desired.

  Another means for improving the adhesion between the ink sheet and the image receiving sheet is to provide a cushion layer that can be softened by heat between the support and the ink layer. As an example of this, the ink layer of the ink sheet and the photothermal conversion layer are applied and dried on a releasable temporary support, and then bonded to the cushion layer, and the interface between the ink layer and the release surface of the temporary support. And a method for producing an ink sheet is disclosed (for example, see Patent Document 2). Although this release layer can be formed by thermosetting various resins, there is a high demand for management conditions for thermosetting, and if the strict thermosetting control is not performed, the release layer may become an ink layer or an intermediate layer due to insufficient curing. There has been a problem that the layer solvent swells to cause a coating failure such as a scratch at the time of coating, or a surface energy is excessively lowered due to overcuring and a cissing failure occurs at the time of coating an ink layer or an image receiving layer. Further, the phosphoric ester fluorine compound used as a mold release agent has a problem that there is a concern about the adverse effect on the natural environment, like the above-mentioned certain types of fluorine surfactants.

Therefore, as shown in Japanese Patent Application No. 2004-165572 (filed on June 3, 2004), a natural environment can be obtained by using a “perfluoroalkyl acrylate-containing polymer” in place of the conventionally used perfluoroalkyl phosphate ester. Ink sheet using a temporary support that does not require strict thermal curing control and does not cause repelling even under excessive curing conditions. However, there has been a new problem that dot gain (DG) fluctuates with respect to the temperature and humidity environment during exposure.
JP 2002-347353 A Japanese Patent Laid-Open No. 8-197860

  The present invention has been made in view of the above circumstances, and the object of the present invention is that the sensitivity does not decrease even when stored for a long period of time, and does not adversely affect the natural environment or the human body. By using this release layer, it is possible to provide an ink sheet that does not decrease the dot gain value even at low temperatures and low humidity, and has good fine line reproducibility, and a multicolor image forming method using a plurality of the ink sheets. There is.

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

(Claim 1)
Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In an image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, the ink layer is branched into molecules. An ink sheet comprising a surfactant having a fluoroalkyl group.

(Claim 2)
Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In an image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, two ink layers are contained in the molecule. An ink sheet comprising a surfactant having the above perfluoroalkyl group.

(Claim 3)
Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In the image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, the ink layer has 1 to 6 carbon atoms. An ink sheet comprising a surfactant having a perfluoroalkyl group.

(Claim 4)
Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In an image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, the ink layer has the following general formula (1) An ink sheet comprising at least one surfactant represented by (7) to (7).

The general formula ₍₁₎ Rf 1 -OR 1
Formula _{(2) Rf 1 -O-L} -Rf 1

In the general formulas (1) to (4), Rf ₁ represents a [(CF ₃ ) ₂ C] ₂ C═C (CF ₃ ) — group or a (CF ₃ ) ₂ C═C (C ₂ F ₅ ) — group. L represents a linking group, and R ₁ represents a polar group. a, b, c, d, e, f and g each represent an integer of 1 to 40.

In Formula (5) ~ (7), Rf 2 represents a perfluoroalkyl group having 1 to 7 carbon atoms, R ₂ represents a polar group. m1, m2, m3 and n1 each represents an integer of 1 to 40.

(Claim 5)
Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In an image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, the ink layer has the following general formula (8) An ink sheet comprising at least one of an acetylene glycol-based surfactant or a silicone-based surfactant represented by

In the formula, each of R ^{1 to} R ⁴ represents a hydrogen atom, a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. , EO represents an ethyleneoxy group which may be substituted, and m and n each represent an integer of 0-50.

(Claim 6)
The ink sheet according to claim 1, wherein the ink layer is at least four types of yellow, magenta, cyan, black, and white.

(Claim 7)
After pasting the cushion layer surface and the light-to-heat conversion layer surface of the temporary support on which the release layer, the ink layer, and the light-to-heat conversion layer are coated in this order, and the cushion layer on another support are coated The ink sheet according to any one of claims 1 to 6, wherein the ink sheet is prepared by peeling a temporary support provided with a release layer.

(Claim 8)
The release layer contains at least one homopolymer or copolymer of a polymerizable fluorine compound having (perfluoroalkyl group or perfluoroalkenyl group) and (acrylic acid group or methacrylic acid group) in the molecule. The ink sheet according to claim 7.

(Claim 9)
A multicolor image forming method using the image forming material according to any one of claims 1 to 8, wherein the image recording density of the irradiated laser beam is 2,000 dpi (dpi is 1 inch, that is, dots per 2.54 cm). The image forming method, wherein

(Claim 10)
The image forming method according to claim 9, wherein a recording area of the multicolor image is 500 × 600 mm or more.

  By implementing the present invention, the sensitivity does not decrease even when stored for a long period of time, and the natural environment and the human body are not adversely affected. Further, when the release layer according to claims 7 and 8 is used, dot gain can be achieved even at low temperatures and low humidity. The value does not decrease, and the fine line reproducibility is also good.

  Hereinafter, the image forming material (ink sheet and image receiving sheet) and the image forming method of the present invention will be sequentially described in detail.

<Ink sheet>
The ink sheet used for the image forming material of the present invention is a film having a photothermal conversion function and an ink (coloring material) transfer function, and a photothermal conversion layer and an ink layer having at least a photothermal conversion function on one surface of a support. It is also possible to provide both of these functions to the same layer. If necessary, a cushion layer, a release layer or the like can be provided between these layers and the support, and a back coat layer can be provided on the surface opposite to these layers.

(Support)
The support for the ink sheet may be anything as long as it has rigidity, good dimensional stability, excellent smoothness, and can withstand the heat during image formation. Specifically, paper, coated paper, synthetic paper Various papers such as (polypropylene, polystyrene, or composite materials obtained by bonding them to paper), vinyl chloride resin sheet, ABS resin sheet, polyethylene terephthalate (PET) film, polybutylene terephthalate film, polyethylene naphthalate (PEN) ) Film, Polyacrylate film, Polycarbonate (PC) film, Polyetherketone film, Polysulfone film, Polyethersulfone film, Polyetherimide film, Polyimide film, Polyethylene (PE) film, Polypropylene (PP) film, Polystyrene (PS) film, syndiotactic polystyrene (sPS) film, stretched nylon (Ny) film, polyacetate film, polymethylmethacrylate (PMMA) film, etc., or various plastic films or sheets in which two or more layers are laminated A film or sheet formed of various metals, a film or sheet formed of various ceramics, a metal plate of aluminum, stainless steel, chromium, nickel, etc., or a metal thin film laminated on resin-coated paper or What was vapor-deposited is mentioned.

  These supports can be subjected to various processes such as dimensional stabilization and antistatic. Antistatic agents include cationic, anionic, nonionic surfactants, polymeric antistatic agents, conductive fine particles, as well as “11290 Chemical Products”, Chemical Industries Daily, pages 875-876, etc. Compounds are widely used.

  Further, these supports may be subjected to a conventionally known surface modification treatment. Examples of these surface modification treatments include flame emission treatment, sulfuric acid treatment, corona discharge treatment, plasma treatment, glow discharge treatment and the like. In addition, an adhesive layer may be provided on the support in order to satisfactorily apply each layer described later on the support. A conventionally well-known thing can be especially used as a contact bonding layer without a restriction | limiting. Examples of the method for providing the adhesive layer include water-based resin coating, solvent-based resin coating, water-based latex coating, and hot melt coating.

  In general, it is advantageous to provide an adhesive layer at the time of preparing the support from the viewpoints of cost, stability, etc. From this point, for example, acrylic resin, polystyrene resin, polyester resin, urethane resin, polyethylene / vinyl acetate resin A method of applying latex such as is preferable, but not particularly limited thereto. Such base films with an adhesive layer are available from various companies and can be suitably used.

  In the present invention, since an image is formed by irradiating a laser beam from the ink sheet side, it is desirable that the support for the ink sheet is transparent. The thickness of the support for the ink sheet is preferably thinner than the thickness of the image receiving sheet described later, and is generally about 30 to 150 μm, more preferably 50 to 100 μm, from the viewpoint of easy superposition.

(Photothermal conversion layer)
The photothermal conversion layer contains a photothermal conversion substance, a binder, and, if necessary, a matting agent, and further contains other components (a surfactant, a thickener, an antistatic agent, etc.) as necessary.

  The photothermal conversion substance is a substance having a function of converting irradiated light energy into heat energy. Although it varies depending on the light source, a substance that absorbs light and efficiently converts it into heat is good.For example, when a semiconductor laser is used as a light source, a substance having an absorption band in the near infrared is preferable. For example, organic compounds such as carbon black, cyanine-based, polymethine-based, azurenium-based, squalium-based, thiopyrylium-based, naphthoquinone-based, anthraquinone-based dyes, phthalocyanine-based, azo-based, and thioamide-based organic metal complexes are preferably used. Specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-280750, JP-A-1-293342, JP-A-2-2074, JP-A-3-26593, 3-30991, 3-34891, 3-36093, 3-36094, 3-36095 Same 3-42281 JP, same 3-97589 Patent, compounds described in the 3-103476 Patent and the like. These can be used alone or in combination of two or more.

  The film thickness of the photothermal conversion layer is preferably from 0.1 to 3 μm, more preferably from 0.2 to 1.0 μm. The content of the photothermal conversion substance in the photothermal conversion layer is usually determined such that the absorbance at the wavelength of the light source used for image recording is 0.3 to 3.0, more preferably 0.7 to 2.5. it can. When carbon black is used as the light-to-heat conversion layer, if the film thickness of the light-to-heat conversion layer exceeds 1 μm, the sensitivity tends to decrease instead of causing the ink layer to be overheated. Since it changes depending on the absorbance of the photothermal conversion layer, it may be selected as appropriate.

  As the binder contained in the photothermal conversion layer, a resin having a high glass transition point (Tg) and high thermal conductivity, such as polymethyl methacrylate, polycarbonate, polystyrene, ethyl cellulose, nitrocellulose, polyvinyl alcohol, polyvinyl chloride, polyamide, General heat-resistant resins such as polyimide, polyetherimide, polysulfone, polyethersulfone, and aramid, and polythiophenes, polyanilines, polyacetylenes, polyphenylenes, polyphenylene sulfides, polypyrroles, and derivatives thereof, or Polymer compounds consisting of these mixtures can be used. Polyamideimides represented by general formula (I) described in JP-A No. 2004-142248, specifically, compounds (1) to (22) in paragraphs “0073” to “0074” are also suitable.

  Water-soluble polymers can also be used. The water-soluble polymer is preferable in that it has good releasability from the ink layer, good heat resistance during laser irradiation, and little scattering even when excessively heated. When a water-soluble polymer is used, it is desirable that the photothermal conversion substance is modified to be water-soluble (for example, by introduction of a sulfo group) or dispersed in water.

  Examples of the matting agent contained in the photothermal conversion layer include inorganic fine particles and organic fine particles. Examples of the inorganic fine particles include silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, barium sulfate, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, boron nitride and other metal salts, kaolin, clay, talc, zinc white, Lead white, sieglite, quartz, diatomaceous earth, barlite, bentonite, mica, synthetic mica and the like can be mentioned. Examples of the organic fine particles include resin particles such as fluorine resin particles, guanamine resin particles, acrylic resin particles, styrene-acrylic copolymer resin particles, silicone resin particles, melamine resin particles, and epoxy resin particles.

The particle size of the matting agent is usually 0.3 to 30 μm, preferably 0.5 to 20 μm, and the addition amount is preferably 0.1 to 100 mg / m ² .

  In addition to this, a vapor deposition layer can also be used as the photothermal conversion layer. Carbon black, gold, silver, aluminum, chromium, nickel, antimony, tellurium, bismuth described in JP-A-52-20842, In addition to a metal black vapor deposition layer such as selenium, metal elements of groups 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 15, 16 of the periodic table, and alloys thereof, or these An alloy of these elements and an alloy layer of elements 1, 2 and 3 or a mixture thereof, and particularly desirable metals include Al, Bi, Sn, In or Zn and alloys thereof, or these metals. And alloys of elements of Groups 1, 2 and 3 of the Periodic Table, or mixtures thereof. Suitable metal oxides or sulfides include Al, Bi, Sn, In, Zn, Ti, Cr, Mo, W, Co, Ir, Ni, Pb, Pt, Cu, Ag, Au, Zr or Te compounds. Or a mixture thereof. Furthermore, the vapor deposition layer of metal phthalocyanines, metal dithiolenes, and anthraquinones is also mentioned. The film thickness of the vapor deposition layer is preferably within 500 mm. The photothermal conversion substance may be the color material itself of the ink layer, and is not limited to the above, and various substances can be used.

  The photothermal conversion layer is preferably provided between the support and the ink layer, more preferably between the cushion layer and the ink layer.

  If the photothermal conversion layer is inferior in adhesion to the lower layer of the support, it may cause film peeling and color turbidity when peeling the transfer material from the image receiving sheet during light irradiation or after thermal transfer. It is also possible to provide an adhesive layer between the two.

  As the adhesive layer, it is necessary to select a material so that the adhesive strength between the photothermal conversion layer and the adhesive layer and the support lower layer at the time of ink transfer is greater than the ink peel strength at the time of ink transfer. Generally, conventionally known adhesives such as polyester, urethane, and gelatin can be used. In order to obtain the same effect, a tackifier and an adhesive can be added to the lower layer of the support instead of providing the adhesive layer. When the adhesive layer is poor in heat softening property or thermoplasticity, the effect of heat softening property is reduced. Therefore, the adhesive layer is preferably as thin as possible. The preferred film thickness is 0.5 μm or less, but not limited to this as long as the adhesive layer can fulfill the purpose of the thermal softening layer.

(Cushion layer)
In order to improve the adhesion between the recording material and the image receiving material at the time of exposure, it is preferable to have a cushion layer or use a cushioning support.

The cushion layer is provided for the purpose of increasing the adhesion between the ink sheet and the image receiving sheet. This cushion layer is a layer having heat softening properties or elasticity, and a material that can be sufficiently softened and deformed by heating, a material having a low elastic modulus, or a material having rubber elasticity may be used. The cushion layer is a layer having a cushioning property, and an elastic modulus and a penetration can be used as a guideline representing the cushioning property here. For example, the elastic modulus at 25 ° C. is about 9.8 × 10 ^{6 to} 24.5 × 10 ⁸ Pa, or the penetration according to JIS K2530-1976 is about 15 to 500, more preferably about 30 to 300. It has been confirmed that this layer exhibits a cushioning property suitable for the formation of a color proof image for color proofing, but the required level varies depending on the intended use of the image, so it should be selected as appropriate. Can do. The cushion layer preferably has a TMA softening point of 70 ° C or lower, more preferably 60 ° C or lower.

  The preferred properties of the cushion layer are not necessarily specified only by the type of the material, but preferred properties of the material itself include polyolefin resins, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, polybutadiene resins. , Styrene-butadiene copolymer (SBR), styrene-ethylene-butene-styrene copolymer (SEBS), acrylonitrile-butadiene copolymer (NBR), polyisoprene resin (IR), styrene-isoprene copolymer (SIS) ), Acrylate copolymer, polyester resin, polyurethane resin, acrylic resin, butyl rubber, polynorbornene and the like. Among these, those having a relatively low molecular weight are likely to satisfy the preferable requirements, but are not necessarily limited in relation to the material.

  The cushion layer can be provided by solvent application, but can also be formed by application in the form of an aqueous dispersion such as latex or emulsion. In addition, a water-soluble resin can also be used. These resins can be used alone or as a mixture as required. Moreover, even if it is a raw material other than the above, a preferable characteristic can be provided to the cushion layer by adding various additives. Examples of such additives include low melting point substances such as wax, plasticizers, and the like. Specific examples include phthalic acid esters, adipic acid esters, glycol esters, fatty acid esters, phosphoric acid esters, chlorinated paraffins, and the like. In addition, various additives described in, for example, “Practical Handbook for Additives for Plastics and Rubber”, Chemical Industry Co., Ltd. (published in 1970) can be added. The additive amount and the like of these additives may be selected in an amount necessary for expressing preferable physical properties in combination with the base cushion layer material, and is not particularly limited. It is preferably at most 5 mass%.

  As a method for forming the cushion layer, a solution obtained by dissolving the material in a solvent or dispersed in a latex form, a coating method such as a blade coater, a roll coater, a bar coater, a curtain coater, or a gravure coater, an extrusion lamination method using hot melt, etc. Applicable. It is also possible to use a void-structure resin layer obtained by foaming a heat softening or thermoplastic resin as a special cushion layer. The film thickness of the cushion layer is preferably 0.5 to 10 μm, more preferably 1 to 7 μm.

(Ink layer)
The ink layer contains at least a pigment for forming an image by being transferred to the image receiving sheet, and further contains a binder for forming the layer and other components as required. Pigments are generally classified into organic pigments and inorganic pigments. The former is particularly excellent in transparency of the coating film, and the latter is generally excellent in hiding properties. That's fine.

  When the ink sheet is used for proofreading printing colors, organic pigments that match or are close in color tone to yellow, magenta, cyan, and black generally used for printing inks are preferably used. In addition, metal powder, fluorescent pigments, etc. may be used. Examples of pigments that can be suitably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. The pigments used in the ink layer are listed below according to hue, but are not limited thereto.

1) Yellow pigment Pigment Yellow (Pigment Yellow) 12 (C.I. No. 21090)
Pigment Yellow 13 (C.I. No. 21100)
Pigment Yellow 14 (C.I.No. 21095)
Pigment Yellow 17 (C.I.No. 21105)
Pigment Yellow 155
Pigment Yellow 180 (C.I.No. 21290)
Pigment Yellow 139 (C.I.No. 56298)
2) Magenta pigment Pigment Red 57: 1 (C.I.No. 15850: 1)
Pigment Red 122 (C.I.No. 73915)
Pigment Red 53: 1 (C.I. No. 15585: 1)
Pigment Red 48: 1 (C.I. No. 15865: 1)
Pigment Red 48: 2 (C.I.No. 15865: 2)
Pigment Red 48: 3 (C.I.No. 15865: 3)
Pigment Red 177 (C.I.No. 65300)
3) Cyan Pigment Pigment Blue (Pigment Blue) 15 (C.I.No. 74160)
Pigment Blue 15: 1 (C.I.No. 74160)
Pigment Blue 15: 2 (C.I.No. 74160)
Pigment Blue 15: 3 (C.I. No. 74160)
Pigment Blue 15: 4 (C.I.No. 74160)
Pigment Blue 15: 6 (C.I.No. 74160)
Pigment Blue 60 (C.I.No. 69800)
4) Black pigment Pigment Black 7 (carbon black)
Further, as pigments that can be used in the present invention, refer to Pigment Handbook: Edited by Japan Pigment Technology Association, Seibundo Shinkosha, 1989, COLOR INDEX, THE SOCIETY OF DYES & COLORIST, THIRD EDITION, 1987, etc. You can select a product.

  The average particle diameter of the pigment is preferably 0.03 to 1 μm, more preferably 0.05 to 0.5 μm. If the particle size is less than 0.03 μm, the dispersion cost may increase or the dispersion may gel. On the other hand, if it exceeds 1 μm, coarse particles in the pigment will adhere to the ink layer and the image receiving layer. May be inhibited, and transparency of the ink layer may be inhibited.

  The content of the colorant in the ink layer may be adjusted so as to obtain a desired concentration with a desired coating film thickness, and is not particularly limited, but is usually in the range of 5 to 70% by mass, preferably 10 -60 mass%.

  Examples of the binder for the ink layer include a heat-meltable material, a heat-softening material, and a thermoplastic resin. The hot-melt material is usually a solid or semi-solid material having a melting point measured using Yanagimoto MJP-2 type in the range of 40 to 150 ° C. Specifically, plant waxes such as carnauba wax, wood wax, aucuric wax and espal wax; animal waxes such as beeswax, insect wax, shellac wax and whale wax; paraffin wax, microcrystal wax, polyethylene wax, ester wax, acid Petroleum waxes such as waxes; and waxes such as mineral waxes such as montan wax, ozokerite, and ceresin. Besides these waxes, palmitic acid, stearic acid, margaric acid, behenic acid, etc. Higher fatty acids; higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate, myricyl stearate; , Amides propionic acid, palmitic acid amide, stearic acid amides such as amide wax; and stearylamine, behenylamine, like higher amines such as palmityl amine.

  Thermoplastic resins include ethylene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, vinyl chloride resins, cellulose resins, rosin resins, polyvinyl alcohol resins. Examples thereof include resins, polyvinyl acetal resins, ionomer resins, petroleum resins, and resins for ink layer binders described in JP-A-6-312583. In particular, resins having a melting point or softening point of 70 to 150 ° C. are preferably used. It is done.

  In addition to the above thermoplastic resins, elastomers such as natural rubber, styrene butadiene rubber, isoprene rubber, chloroprene rubber, and diene copolymer; rosin derivatives such as ester gum, rosin maleic resin, rosin phenol resin, and hydrogenated rosin And high molecular compounds such as phenol resin, terpene resin, cyclopentadiene resin, and aromatic hydrocarbon resin can also be used.

  By appropriately selecting the heat-melting substance and the thermoplastic substance, it is possible to form an ink layer having a desired heat softening point or a heat-transfer point and having a heat transfer property.

  In the present invention, an image can be formed by ablation transfer by using a binder having high thermal decomposability. Such binders include polymeric materials that undergo rapid acid-catalyzed partial degradation, preferably at temperatures below 200 ° C. when measured under equilibrium conditions, such as nitrocelluloses, polycarbonates and J.A. M.M. J. et al. Frechet, F.M. Bouchard, J.A. M.M. Houlihan, B.H. Kryczke and E.I. Eichler, J. et al. Polymers of the type reported in Imaging Science, 30 (2), pages 59-64 (1986), and polyurethanes, polyesters, polyorthoesters, and polyacetals, and their Copolymers are included. Further, these polymers are shown in detail in the report of Holyhan et al.

  Although it is disclosed in JP-A-62-158092 that a high concentration can be obtained by making the particle diameters of the pigments uniform, various dispersants can be used in order to ensure the dispersibility of the pigment and obtain a good color reproduction. It is effective to use.

  Other additives include a plasticizer that increases the sensitivity by plasticizing the ink layer, a surfactant that improves the coatability of the ink layer, and submicron to micron order particles that prevent blocking of the ink layer. (Matting agent) can be added.

  A preferable thickness of the ink layer is 0.2 to 2 μm, and more preferably 0.3 to 1.5 μm. In particular, it has been confirmed that high sensitivity can be obtained when the thickness is 0.8 μm or less. However, since the thin film transferability of the ink layer varies depending on the type of binder and colorant used, the mixing ratio thereof, etc., an optimum film The thickness range is selected according to the balance between sensitivity and resolution, and other desired image reproduction performance.

(Surfactant)
In the present invention, the ink layer contains a specific surfactant. That is, a) a surfactant having a branched perfluoroalkyl group in the molecule, b) a surfactant having two or more perfluoroalkyl groups in the molecule, and c) a perfluoroalkyl group having 1 to 6 carbon atoms. D) a surfactant represented by the general formulas (1) to (7), e) an acetylene glycol surfactant or a silicone surfactant represented by the general formula (8). Of these, d) and e) are preferred. In addition, about a), b), and c), the commercial item of a Neos company or an omnova company is applicable.

In the general formulas (1) to (4), examples of the linking group represented by L include divalent groups such as alkylene, alkyleneoxy, and phenylene, and an alkyleneoxy group having 1 to 4 carbon atoms is particularly preferable. Examples of the polar group represented by R ₁ include a hydrogen atom, an organic group containing a hydroxyl group, an alkyl carboxylate, a benzene carboxylate, an alkyl benzene carboxylate, an alkyl ammonium salt, a benzene ammonium salt, and an alkyl benzene ammonium salt. . a to g each represents an integer of 1 to 40, preferably 5 to 25.

Formula (5), (6), in (7), Rf ₂ is a perfluoroalkyl group having 1 to 7 carbon atoms, preferably a _{C 2 F 5 ~C 5 F 11} . m1, m2, m3 and n1 each represents an integer of 1 to 40, preferably 2 to 10.

  In the following, typical examples of the fluorine-based surfactants represented by the general formulas (1) to (7) are shown, but the invention is not limited thereto.

In the general formula (8), examples of the alkyl group represented by R ^{1 to} R ⁴ include groups such as methyl, ethyl, propyl group, i-propyl, butyl group, i-butyl group, and cyclohexyl. Specific examples of the aryl group include groups such as phenyl and naphthyl. m and n are preferably integers of 0 to 4.

Among these, R ² and R ³ are methyl groups, R ¹ and R ⁴ are i-butyl groups, and m and n are preferably 0.

  Specific examples of the acetylene glycol represented by the general formula (8) are given below.

The content of the acetylene glycol surfactant in the ink layer is preferably in the range of 0.005 to 0.2 g / m ² as the solid content in the applied ink layer. 0.1 g / m ² is more preferable.

  The silicone-based surfactant is a water-soluble compound in which a hydrophobic portion is made of a silicone resin, and a hydrophilic group is introduced into the terminal and / or side chain thereof. Typical examples of the silicone resin include poly (dimethyl) siloxane, methylphenyldimethylpolysiloxane, tetramethyltetraphenylpolysiloxane, dimethylpolysiloxane / polymethylphenylsiloxane copolymer, polymethylsiloxane, tetramethylpolymethylsiloxane, Examples thereof include polymethylsiloxane / polydimethylsiloxane copolymer in which a part or all of the side chain methyl groups are substituted with phenyl groups, hydrogen atoms, or the like. (However, among the above notations, a silicone resin having a low degree of polymerization is also included. For example, tetramethyltetraphenyltrisiloxane is also included in tetramethyltetraphenylpolysiloxane.) In addition, a hydrophilic group introduced into this silicone resin. Examples thereof include polyether groups, polyglycerin groups, pyrrolidone groups, betaine groups, sulfate groups, hydroxyl groups, carboxyl groups, phosphate groups, quaternary ammonium groups, and the like.

  These silicone resins and hydrophilic groups can be used in appropriate combination. In addition, regarding the structure of the surfactant, not only a hydrophilic group is simply introduced into the terminal and / or side chain of the above-mentioned silicone resin, but also a polymer in which a hydrophilic group is introduced and a polymer in which a hydrophilic group is not introduced are randomly copolymerized and blocked. It may be copolymerized by copolymerization.

  Specifically, for example, manufactured by Shin-Etsu Chemical Co., Ltd .: KF351 (A), KF352 (A), KF353 (A), KF354 (A), KF355 (A), KF615 (A), KF618, KF945 (A), KF6001, KF6004, KF6012, KF6013, KF6015, KF6016, KF6017, KF640, KF641, KF700, X-22-4959, X-22-4966, etc., manufactured by Toray Dow Corning Silicone: SYLGARD309, SH3746, SH3749, SH3749 SH8400, SH8410, SH8700, etc., manufactured by Nihon Unicar Corporation: SILWETL-77, L-720, FZ2122, L-7001, L-7002, FZ-2123, L-7604, FZ-2105, FZ-2104, FZ-211 , FZ-2110, FZ-2161, FZ-2162, FZ-2163, FZ-2164 and the like. Among these, a silicone surfactant in which polydimethylsiloxane is introduced as a silicone resin and a polyether group, polyglycerin group, or pyrrolidone group is introduced as a hydrophilic group is preferable.

The content of the silicone-based surfactant in the ink layer is preferably in the range of 0.005 to 0.20 g / m ² as the solid content in the applied ink layer. 10 g / m ² is more preferable.

  Further, the silicone surfactant and the acetylene glycol surfactant may be used in combination, and the mixing ratio in that case is preferably silicone: acetylene glycol = 1: 10 to 10: 1, and 1: 5 5: 1 is more preferred.

(Back coat layer)
For the backcoat layer of the ink sheet, the same binder as in the image receiving sheet described later can be used. The back coat layer preferably contains a matting agent.

As the matting agent preferably added to the backcoat layer, organic or inorganic fine particles can be used. Examples of the organic matting agent include polymethyl methacrylate, polystyrene, polyethylene, polypropylene, fine particles of other radical polymerization polymers, and fine particles of condensation polymers such as polyester and polycarbonate. The back coat layer is preferably provided at a weight of about 0.5 to 5 g / m ² . If it is less than 0.5 g / m ² , the coating property is unstable, and problems such as powdering off of the matting agent are likely to occur. In addition, when the coating is applied greatly exceeding 5 g / m ² , the particle size of a suitable matting agent becomes very large, and the ink layer surface is embossed by the back coat during storage, particularly in thermal transfer for transferring a thin ink layer. The recorded image is likely to be missing or uneven. The matting agent preferably has a number average particle diameter that is 1 to 20 μm larger than the film thickness of only the binder of the backcoat layer. Among the matting agents, 1 mg / m ² or more of particles having a particle diameter of 2 μm or more are required, and preferably ² to 600 mg / m ² . This in particular improves foreign matter failures. Further, by using a narrow particle size distribution such that a value σ / rn (= coefficient of variation of the particle size distribution) obtained by dividing the standard deviation of the particle size distribution by the number average particle size is 0.3 or less, Defects generated by particles having an abnormally large particle size can be improved, and desired performance can be obtained with a smaller addition amount. The variation coefficient is more preferably 0.15 or less.

  An antistatic agent is preferably added to the backcoat layer in order to prevent adhesion of foreign matters due to frictional charging with the transport roll during sheet supply. Antistatic agents include cationic surfactants, anionic surfactants, nonionic surfactants, polymer antistatic agents, and conductive fine particles, as well as “11290 chemical products”, Chemical Industry Daily, 875- The compounds described on page 876 and the like are widely used. Among the above substances, metal oxides such as carbon black, zinc oxide, titanium oxide and tin oxide, and conductive fine particles such as organic semiconductors are preferably used. In particular, it is preferable to use conductive fine particles because the antistatic agent is not dissociated from the backcoat layer and a stable antistatic effect can be obtained regardless of the environment. In addition, various activators, release agents such as silicone oil, fluorine-based resins, and the like can be added to the backcoat layer in order to impart applicability and releasability. As the activator, the activator of the ink layer can be used, and as the fluororesin, a fluoropolymer described in detail in a release layer described later can be used. The back coat layer is particularly preferable when the softening point measured by TMA of the cushion layer and the image receiving layer is 70 ° C. or less.

  Next, at least one of the polymerizable compounds having (perfluoroalkyl group or perfluoroalkenyl group) and (acrylic acid group or methacrylic acid group) contained in the release layer of the temporary support according to claims 7 and 8. The species homopolymer or copolymer (hereinafter referred to as the fluoropolymer of the present invention) will be described.

(Fluoropolymer)
The fluoropolymer of the present invention is a copolymer of a polymerizable compound having (perfluoroalkyl group or perfluoroalkenyl group) and (acrylic acid group or methacrylic acid group) and another polymerizable compound copolymerizable with the polymerizable compound. The polymerizable compound having (perfluoroalkyl group or perfluoroalkenyl group) and (acrylic acid group or methacrylic acid group) is preferably 25% by mass or more, more preferably 40% by mass or more based on the copolymer. More preferably.

  Examples of the polymerizable compound having (perfluoroalkyl group or perfluoroalkenyl group) and (acrylic acid group or methacrylic acid group) include the following acrylates and methacrylates.

RfSO ₂ N (R ¹ ) LOCOCR ² = CH ₂
Rf (CH ₂ ) _n OCOCR ² ═CH ₂
RfCON (R ¹ ) LOCOCR ² = CH _{2
RfCH 2 CH (OH) CH 2} OCOCR 2 = CH 2
_{RfCH 2 CH (OCOCH 3) CH} 2 OCOCR 2 = CH 2
RfOArCH ₂ OCOCR ² ═CH ₂
In the formula, Rf is a perfluoroalkyl group or perfluoroalkenyl group having 3 to 21 carbon atoms, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, L is an alkylene group having 1 to 10 carbon atoms, and R ² is hydrogen. An atom or a methyl group, Ar represents an aryl group which may have a substituent, and n represents an integer of 1 to 10.

  More specifically, the following compounds can be exemplified.

C ₈ F ₁₇ CH ₂ OCOCH═CH _{2
C 7 F 15 CH 2 OCOC (} CH 3) = CH 2
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCH═CH _{2
C 8 F 17 CH 2 CH 2} OCOC (CH 3) = CH 2
C ₈ F ₁₇ CH ₂ CH ₂ OCOCH═CH ₂
C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCH═CH _{2
C 8 F 17 SO 2 N (} C 2 H 5) CH 2 CH 2 OCOC (CH 3) = CH 2
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH═CH _{2
p-C 9 F 19 -C 6} H 4 -CH 2 OCOCH = CH 2
_{p-C 6 F 13 -C 6} H 4 -CH 2 OCOC (CH 3) = CH 2
There are various kinds of polymerizable compounds other than those described above that can be copolymerized. For example, (1) (meth) acrylic acid and their methyl, ethyl, butyl, i-butyl, t-butyl, propyl, 2- Ethylhexyl, hexyl, decyl, lauryl, stearyl, i-bornyl, β-hydroxyethyl, glycidyl, phenyl, benzyl, 4-cyanophenyl esters, (2) acetic acid, propionic acid, caprylic acid, lauric acid, stearic acid, etc. Fatty acid vinyl esters, (3) Styrene compounds such as styrene, α-methylstyrene, p-methylstyrene, (4) Halogenation of vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, etc. Fats such as vinyl or vinylidene compounds, (5) allyl heptanoate, allyl caprylate, allyl caproate Acid allyl esters, (6) vinyl alkyl ketones such as vinyl methyl ketone and vinyl ethyl ketone, (7) acrylamides such as N-methyl acrylamide and N-methylol methacrylamide, and (8) 2,3-dichloro Examples include dienes such as -1,3-butadiene and isoprene.

  The polymerization initiator used for the polymerization of the polymerizable compound is a water-soluble azo hydrochloride or sulfate having a polymerization initiation temperature of 50 ° C. or lower. The polymerization start temperature is a temperature at which the polymerization initiator halves in 10 hours in water (or an organic solvent such as alcohol). The polymerization initiation temperature may be 50 ° C. or lower, for example, 30 to 50 ° C. The water-soluble azo hydrochloride or sulfate may be a hydrochloride or sulfate of a compound having an azo group and an imidazolinyl group. The imidazolinyl group may be substituted (such as methyl substitution) or unsubstituted.

  Specific examples of the polymerization initiator include 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-methyl-2- Imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, and the like.

  It is preferable that the quantity of a polymerization initiator is used in 0.01-2.0 mass parts, for example, 0.1-1.0 mass part with respect to 100 mass parts of monomers which form a polymer.

  The surfactant used to disperse the polymer may be any of nonionic, anionic and cationic surfactants, and a mixture of a cationic surfactant and a nonionic surfactant. May be included.

  Examples of organic solvents for dispersing the polymer include acetone, ketones such as methyl ethyl ketone, ethylene glycol derivatives such as ethylene glycol and polyethylene glycol, and ethylene glycol derivatives such as polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, and polyethylene glycol monobutyl ether. Alkyl ethers, propylene glycol derivatives such as propylene glycol, dipropylene glycol, and polypropylene glycol, polyethers such as cyclodextrin and dextrin, and esters of methyl acetate and ethyl acetate. The amount of the organic solvent is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, per 100 parts by mass of the polymer. Most preferred is 20 to 80 parts by mass.

  In order to produce the dispersion of the polymer of the present invention, a polymerizable compound is emulsion-polymerized in water containing an organic solvent in the presence of a polymerization initiator and a surfactant to obtain a polymer emulsion. . If necessary, add water and / or surfactant to the emulsion. The polymerization temperature is preferably 40 to 90 ° C., for example 45 to 60 ° C., for example (polymerization start temperature of the polymerization initiator−10 ° C.) to (polymerization start temperature of the polymerization initiator + 10 ° C.). It is preferable that the polymerization start temperature of the initiator is −2 ° C.) to (the polymerization start temperature of the polymerization initiator + 5 ° C.). The polymerization time is preferably 0.5 to 20 hours, and more preferably 2 to 10 hours.

  The polymer of the present invention is preferably applied to a cross-linked mold release layer that undergoes a cross-linking treatment at the same time as coating or after coating, but can also be applied to a non-cross-linked mold release layer that is not subjected to cross-linking treatment. . The cross-linking method in the case of forming the cross-linking release layer may be either a method using a thermosetting reaction or a method using a photo-curing reaction, but a method using heat curing that places little load on the coating equipment is preferable. Specifically, it is preferable to convert a resin having a hydroxyl group, a carboxyl group, an ammonium group, or the like into a crosslinked product using a crosslinking agent such as a melamine compound, an isocyanate compound, or a glyoxal derivative.

  In the present invention, the coating solvent for the release layer is not particularly limited, and the fluoropolymer may be dissolved or non-dissolved in the solvent, but the coating solvent is preferably an aqueous solvent, The polymer is preferably a water-dispersible resin obtained by an emulsion polymerization method or a suspension polymerization method.

  In addition, the aqueous solvent in this invention refers to the mixed solvent which consists of a single phase without phase separation in which 50% or more, preferably 70% or more of water or at least the solvent is composed of water. Examples of organic solvents that can be mixed with water include alcohols such as i-propyl alcohol, ethyl alcohol, and methyl alcohol, ketones such as acetone, glycols such as propylene glycol, tripropylene glycol, and diethylene glycol, and dipropylene glycol monomethyl ether. Examples include glycol derivatives.

  The water-dispersible resin in the present invention is polymerized by a conventionally known emulsion polymerization method or suspension polymerization method as shown in JP-A-5-59108, JP-A-2000-256408 and the like, and is 100 μm in an aqueous solvent. It refers to a resin dispersed and stabilized with the following average particle size. Specific examples include styrene acrylic resin emulsions, acrylic resin emulsions, methacrylic resin emulsions, and the like.

  When providing a release layer using an aqueous solvent which is a preferred embodiment of the present invention, it is preferable to use an aqueous resin in addition to the fluoropolymer.

  The aqueous resin in the present invention is obtained by a water-soluble resin having a solubility in pure water at 25 ° C. of 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, or an emulsion polymerization method or a suspension polymerization method. It refers to the obtained water dispersible resin.

  Examples of the water-soluble resin include polyvinyl alcohol (PVA), cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, polyvinyl acetal, cellulose resin [methyl cellulose (MC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose ( CMC) etc.], chitins, chitosans, starch, polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE), polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), poly A material satisfying the above-mentioned solubility can be selected from acrylates, maleic resins, alginates and gelatins. Among the above, polyvinyl alcohols are particularly preferable.

  As the water dispersible resin, in addition to the styrene acrylic resin emulsion, acrylic resin emulsion, and methacrylic resin emulsion, a polyester resin emulsion and a vinyl acetate resin emulsion can also be used.

(Temporary support)
As the base material used for the temporary support, a conventionally known support base material (see the support for the ink sheet) can be used without particular limitation, and the thickness is preferably 6 to 100 μm, more preferably 12. ~ 50 μm.

  Examples of the material include various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material obtained by bonding them with paper), vinyl chloride resin sheet, ABS resin sheet, PET film, polybutylene. Terephthalate film, PEN film, polyarylate film, PC film, polyetherketone film, polysulfone film, polyethersulfone film, polyetherimide film, polyimide film, PE film, PP film, PS film, Ny film, polyacetate film, etc. Single layer, or various plastic films or sheets in which two or more layers are laminated, films or sheets formed of various metals, films or sheets formed of various ceramics, and aluminum Um, stainless steel, chromium, metal plate such as nickel, followed by a metal thin film to the paper was resin coated and laminated or deposited. Among these, polyesters such as PET and PEN, and PP are preferable, and in particular, excellent in shape maintenance including dimensional stability and uniformity of surface shape, and in a wide range of selection of coating solvents, such as PET and PEN. A plastic support made of polyester is preferred.

  Polyester is a general term for polymers having an ester bond as the main bond chain of the main chain, but those having ethylene terephthalate and / or ethylene naphthalate units as main constituent components from the viewpoint of heat resistance, film-forming property, etc. Preferably, the melting point of the polyester is preferably 210 to 280 ° C, more preferably 220 to 270 ° C. Among these, as polyester, PET and PEN are particularly preferably used because they are excellent in strength, heat resistance, water resistance, chemical resistance and the like.

  Further, these temporary supports preferably have a heat shrinkage of preferably 0.01 to 5% in the horizontal direction and 0.01 to 5% (JISC-2323) in the vertical direction.

  These temporary supports can be subjected to various processes such as dimensional stabilization and antistatic. Antistatic agents include cationic surfactants, anionic surfactants, nonionic surfactants, polymer antistatic agents, and conductive fine particles, as well as “11290 chemical products”, Chemical Industry Daily, 875- The compounds described on page 876 and the like are widely used.

  In addition, in this polyester, if necessary, appropriate additives within the range in which the effects of the present invention are not impaired, for example, heat-resistant stabilizer, oxidation-resistant stabilizer, organic lubricant, organic fine particles, filler Further, a nucleating agent, a dye, a dispersing agent, a coupling agent and the like may be blended.

  These temporary supports may be subjected to a conventionally known surface modification treatment. Examples of these surface modification treatments include flame emission treatment, sulfuric acid treatment, corona discharge treatment, plasma treatment, glow discharge treatment and the like. In addition, an adhesive layer may be provided on the temporary support so that the release layer is satisfactorily coated on the temporary support.

<Image-receiving sheet>
Next, an image receiving sheet used in combination with the ink sheet of the present invention will be described as an image forming material.

  The image-receiving sheet has at least an image-receiving layer on the support. If necessary, an intermediate layer such as a thermal softening layer or a release layer is provided between the support and the image-receiving layer, on the side opposite to the image-receiving layer. A back coat layer can be provided on the (back side).

(Support)
As the support for the image receiving sheet, a conventionally known support can be used without particular limitation. The thickness is preferably 30 to 200 μm, more preferably 50 to 150 μm.

  Examples of the support include various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material obtained by bonding them to paper), vinyl chloride resin sheets, ABS resin sheets, polyethylene terephthalate films. , Polybutylene terephthalate film, polyethylene naphthalate film, polyarylate film, polycarbonate film, polyether ketone film, polysulfone film, polyether sulfone film, polyetherimide film, polyimide film, polyethylene film, polypropylene film, polystyrene film, stretched Nylon film, polyacetate film or other single layer, or two or more layers of plastic film or sheet, or various metals Film or sheet, various ceramics such in the formed film or sheet, further, aluminum, stainless steel, chromium, metal plate such as nickel, followed by a metal thin film to the paper was resin coated and laminated or deposited. Among these, polyesters such as polyethylene terephthalate and polyethylene naphthalate and polypropylene are preferable, and a plastic support made of polyester such as polyethylene terephthalate and polyethylene naphthalate is particularly preferable from the viewpoint of dimensional stability.

  Polyester is a general term for polymers that have an ester bond as the main bond chain, but contains ethylene terephthalate and / or ethylene naphthalate units as the main constituent from the viewpoints of heat resistance and film-forming properties. The melting point of the polyester is preferably 210 ° C. to 280 ° C., more preferably 220 to 270 ° C. Among these, as the polyester, polyethylene terephthalate and polyethylene naphthalate are particularly preferably used because they are excellent in strength, heat resistance, water resistance, chemical resistance, and the like.

  These supports preferably have a heat shrinkage of 0.01 to 5% in the horizontal direction and 0.01 to 5% in the vertical direction (JIS C-2323). More preferably, the horizontal and vertical ranges are 0.3 to 2% and 1.2 to 2%, respectively. Further, the tensile strength of the support is preferably 49 to 294 N / mm in the horizontal direction and 98 to 343 N / mm in the vertical direction, and particularly preferably the horizontal and vertical directions are 127.4 to 215.6 N / mm and 147 to 21506 N / mm, respectively. Range. The reason is to prevent wrinkles from moving when an image is transferred to paper.

  These supports can be subjected to various processes such as dimensional stabilization and antistatic. Antistatic agents include cationic, anionic, nonionic surfactants, polymeric antistatic agents, conductive fine particles, as well as “11290 Chemical Products”, Chemical Industries Daily, pages 875-876, etc. Compounds are widely used. Moreover, a conventionally well-known surface modification technique can be used conveniently.

  Further, in this polyester, if necessary, appropriate additives such as a heat-resistant stabilizer, an oxidation-resistant stabilizer, an organic lubricant, organic fine particles, and a filler may be added as long as the effects of the present invention are not impaired. Further, a nucleating agent, a dye, a dispersing agent, a coupling agent and the like may be blended.

  The image-receiving sheet support of the present invention is preferably provided with observation light hiding properties by inorganic particles or organic particles. This facilitates front / back discrimination in the image-receiving sheet after image recording, and can prevent loss due to front / back discrimination errors during image transfer.

(Thermo-softening layer)
Next, the heat softening layer of the image receiving sheet will be described. The thermal softening layer preferably has elasticity without fluidity at room temperature and exhibits remarkable fluidity in a high temperature region exceeding the softening temperature. The thermal softening layer preferably has a TMA (Thermal Mechanical Analysis) softening point of 30 to 100 ° C, more preferably 40 to 80 ° C. Further, the melting point specified in Japanese Patent Application No. 11-243093 is preferably 80 to 150 ° C., and in particular, the difference between the melting point and the TMA softening point is particularly preferably less than 50 ° C. and less than 40 ° C. Is most preferred.

  Preferred properties of the heat-softening layer are not necessarily specified only by the type of material, and are affected by molecular weight, molecular weight distribution, crystal structure, etc., but those having preferred thermal properties as resins are polyethylene, polypropylene, ethylene-vinyl acetate. Copolymer, polyolefin resin such as ethylene-ethyl acrylate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, copolymer of vinyl chloride and polyvinyl alcohol, vinyl acetate-maleic acid copolymer, poly Vinylidene chloride, polybutadiene resin, styrene-butadiene copolymer (SBR), styrene-ethylene-butene-styrene copolymer (SEBS), acrylonitrile-butadiene copolymer (NBR), polyisoprene resin (IR), styrene-isoprene Copolymer (SIS), butyl rubber, etc. Synthetic rubber, chlorinated rubber, acrylic acid ester copolymers, polyester resins, polyurethane resins, acrylic resins, polynorbornene, and the like. Among these, polyolefin resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and vinyl chloride and polyvinyl alcohol. A copolymer and a vinyl acetate-maleic acid copolymer are preferred.

(Image receiving layer)
Next, the image receiving layer will be described. The image receiving layer is composed of a binder and various additives added as necessary. The image receiving layer preferably has a softening point by TMA measurement of 100 ° C. or lower, more preferably 80 ° C. or lower. Specific examples of the image receiving layer binder include adhesives such as polyvinyl acetate emulsion adhesive, chloroprene adhesive, epoxy resin adhesive, natural rubber, chloroprene rubber, butyl rubber, polyacrylate ester, nitrile rubber , Polysulfide, silicone rubber, petroleum resin, etc., recycled rubber, SBR, polybutadiene resin, polyisoprene, polyvinyl ether, ionomer resin, SIS, SEBS, acrylic resin, ethylene copolymer, ethylene-vinyl chloride Copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate resin (EVA), vinyl chloride graft EVA resin, EVA graft vinyl chloride resin, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, etc. , Polyvinylidene chloride, vinylidene chloride Styrene copolymer such as polystyrene, styrene-acrylic acid copolymer, styrene-maleic acid ester copolymer, vinyl acetate copolymer, urethane resin, polyester resin, polyolefin resin, various modified olefins, polyvinyl butyral, phenol Examples thereof include resins, urea resins, melamine resins, alkyd resins, maleic acid resins, hydroxystyrene copolymers, sulfonamide resins, cellulose resins, nylon resins, and polyvinyl formal resins.

  Particularly preferred binders are polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene-vinyl acetate copolymers and ethylene-acrylic acid copolymers, and polyvinyl chlorides such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymers. Copolymers, polyvinylidene chloride, vinylidene chloride copolymers, styrene copolymers such as polystyrene, styrene-acrylic acid copolymers, styrene-maleic acid ester copolymers, and vinyl acetate copolymers. The above binders may be used alone or in combination of two or more.

The image receiving layer preferably contains a matting agent. As the material for the matting agent, those used for the backcoat layer described later can be suitably used. The number average particle size of the matting agent is preferably 0.3 to 10.0 μm, more preferably 0.3 to 8.0 μm larger than the average film thickness of the portion of the image receiving layer where the matting agent is not present. Of these, those larger by 1 to 5.5 μm are effective and particularly preferable. If the thickness is less than 0.3 μm, the effect on fog and gas removability is small, and if it exceeds 10.0 μm, the sensitivity is deteriorated. In addition, those having a distribution in which the particle mass twice or more the number average particle size is 20% or less are preferable, and those having a distribution in which the particle mass twice or more the number average particle size is 5% or less are more preferable. . Those having a distribution in which the particle mass that is twice or more the number average particle diameter is 20% or less is uniformly relieved, so that deterioration in storage stability such as blocking is prevented. It is more preferable in terms of storage stability to use a particle having a distribution in which the particle mass that is twice or more the number average particle diameter is 5% or less. When such a matting agent is selected, if the binder film thickness of the image receiving layer is 3.0 μm or more, the matting agent is too much and a yellowish image is formed. Therefore, the binder film thickness of the image receiving layer is 0. .8 to 3.0 μm is preferable.

The distribution of the matting agent on the surface of the image receiving layer is also important. The number of matting agents on the image receiving layer is preferably 200 to 2400 / mm ² . Further, the fact that the matting agent is spherical makes it possible to effectively improve the performance by adding the matting agent. The true spherical shape means that the shape when the matting agent particles are observed with a microscope or the like is almost spherical, and the difference between the major axis and the minor axis is about 20% or less. Matting with agents of the image receiving layer is preferably from 0.6~4g / m ^2, more preferably 1 to 3 g / m ^2.

(Peeling layer)
The image receiving sheet can be provided with a release layer between the heat softening layer and the image receiving layer. The release layer is preferably composed mainly of a resin having an SP (solubility parameter) value of 1 or more different from the image-receiving layer forming resin. When the SP value is different from 2 to 20, the release property is improved. preferable.
In addition, when the matting agent is used for the image receiving layer / back coat layer, the image forming by pressing with the mat agent of the image receiving layer or the mat agent of the back coat layer when stored in a stacked state is provided. This is a preferable mode for dealing with various types of paper having different irregularities by facilitating peeling due to performance fluctuations due to surface embossing of the material and transferring the image onto the final image carrier.

  It is important to select the binder for the release layer in consideration of the image receiving layer. In the present invention, it is preferable to select resins having SP values different by 1 or more as main components. The SP value is a solubility parameter and is defined by the following equation.

SP = (ΔE / V) ^1/2
Here, ΔE: Evaporation energy V: Molar volume Therefore, since ΔE / V is the cohesive energy density, it can be said that the SP value is an amount related to the cohesive energy of the substance. In the present invention, the SP value was determined by the method of Okitsu described in Adhesion, August issue [Vol. 40, No. 8, Vol. 436], published by Kobunshi Kankokai, pages 6-14.

  Specific release layer materials selected in combination with the image receiving layer include polyester, polyvinyl acetal, polyvinyl formal, polyparabenic acid, polymethyl methacrylate, polycarbonate, ethyl cellulose, nitrocellulose, methylcellulose, carboxymethylcellulose, and hydroxypropylcellulose. , Polyvinyl alcohol, polyethylene oxide, polyvinyl chloride, urethane resin, fluorine-based resin, polystyrene, styrene such as acrylonitrile styrene, and those obtained by crosslinking these resins, polyamide, polyimide, polyetherimide, polysulfone, polyethersulfone, aramid, etc. Thermosetting resins having a Tg of 65 ° C. or higher and cured products of these resins. As the curing agent, general curing agents such as isocyanate and melamine can be used.

<Image forming method>
The laser beam used for light irradiation in the image formation of the present invention is preferably multi-beam light, and particularly preferably a multi-beam two-dimensional array. The multi-beam two-dimensional array uses a plurality of laser beams when recording by laser irradiation, and a plurality of spot arrays of these laser beams are arranged along the main scanning direction and along the sub-scanning direction. A two-dimensional planar array consisting of rows. By using laser light that is a multi-beam two-dimensional array, the time required for laser recording can be shortened. The laser beam used can be used without particular limitation as long as it is a multi-beam, solid state laser beam such as argon laser beam, helium neon laser beam, helium cadmium laser beam, etc., YAG laser beam, semiconductor, etc. Direct laser light such as laser light, dye laser light, and excimer laser light is used. Or the light etc. which converted these laser lights into the half wavelength through the 2nd harmonic element can also be used. In consideration of output power, ease of modulation, etc., it is preferable to use semiconductor laser light.

  An example of a method for forming an image using an ink sheet and an image receiving sheet, which are image forming materials used in the present invention, is as follows. The image receiving sheet and the ink sheet are wound around an exposure drum in order and held by pressure reduction adhesion. A laser beam is irradiated from the back side of the sheet (back coat layer application side) according to the image data, and the ink sheet absorbs the laser beam and converts it into heat, and the image is received from the ink layer of the ink sheet by the converted heat. The image is transferred and formed on the image receiving layer of the sheet.

  When the present invention is applied to a multicolor image forming method, it is preferable to first record an image of a laser melt thermal transfer ink sheet having a color set so that absorption at the exposure wavelength of the ink sheet is maximized. In the laser thermal transfer recording to which the present invention belongs, the thermal transfer ink sheet and the image receiving sheet are brought into close contact (for example, under reduced pressure) and imagewise laser exposure is performed. However, if absorption is large, gas during laser exposure (regardless of the presence or absence of ablation) The amount of occurrence is increased, and the transferability is likely to deteriorate. When repetitively recording a single color image and overlaying multiple colors, transferring from a color with a large amount of gas generation improves adhesion during exposure and stabilizes the sensitivity of the second and subsequent colors. Is also preferable. In particular, it is preferable to transfer black having absorption in the infrared region first. Further, when a multicolor image is formed as a proof image, it is preferable to perform a color matching process as described in JP-A-2002-355997.

  As a method for transferring the image on the image receiving sheet thus formed to the final recording medium, a conventionally known heating / pressure transfer device, for example, a transfer device described in JP-A Nos. 11-268494 and 2002-2641, or The transfer devices described in JP-A-6-238870 and JP-A-10-16188 can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention, the embodiment of this invention is not restrict | limited to these.
Unless otherwise specified, “part” in the examples represents “part by mass” and “%” represents “% by mass”.

Example 1
<Preparation of Black Ink Sheet 1>
<Formation of back coat layer>
(Backcoat first layer coating solution)
Acrylic resin aqueous dispersion (Julimer ET410: Nippon Pure Chemical Industries, solid content 20%)
2.0 parts antistatic agent (aqueous dispersion of tin oxide-antimony oxide, average particle size: 0.1 μm, 17%)
7.0 parts Polyoxyethylene phenyl ether 0.1 part Melamine compound (Sumitex Resin M3: manufactured by Sumitomo Chemical Co., Ltd.) 0.3 part Adjusted to a total amount of 100 parts with distilled water <Formation of first layer of backcoat>
One side (back surface) of a biaxially stretched transparent PET support (thickness of both sides is 0.01 μm) with a thickness of 75 μm is subjected to corona treatment, and the back coat first layer coating solution is dried to a thickness of 0.03 μm. After coating, the film was dried at 180 ° C. for 30 seconds to form a backcoat first layer.
(Backcoat second layer coating solution)
Polyolefin (Chemipearl S-120: Mitsui Petrochemical Co., Ltd., 27%) 3.0 parts Antistatic agent (tin oxide-antimony water dispersion: supra) 2.0 parts Colloidal silica (Snowtex C: Nissan Chemical) Industrial Co., 20%) 2.0 parts Epoxy compound (Dinacol EX-614B: manufactured by Nagase Kasei Co., Ltd.) 0.3 parts Adjusted to a total amount of 100 parts with distilled water <Formation of back coat second layer>
On the first backcoat layer, a backcoat second layer coating solution was applied to a dry layer thickness of 0.03 μm, and then dried at 170 ° C. for 30 seconds to form a backcoat second layer.

<Preparation of coating solution 1 for photothermal conversion layer>
The following components were mixed while stirring with a stirrer to prepare a coating solution 1 for a photothermal conversion layer.
(Coating liquid 1 composition for photothermal conversion layer)
Infrared absorbing dye (NK-2014: Cyanine dye manufactured by Hayashibara Biochemical Laboratories)
7.6 parts Binder resin (compound described in Table 1) 29.3 parts Exon naphtha 5.8 parts N-methyl-2-pyrrolidone (NMP) 1500 parts Methyl ethyl ketone (MEK) 360 parts Fluorosurfactant (FC-4129) 0.5 part mat agent dispersion liquid * 14.1 parts * Mat agent dispersion liquid: NMP 69 parts, MEK 20 parts, styrene acrylic resin (John Crill 611: Johnson Polymer Co., Ltd.) 3 parts, silica (Seahoster KE-P150: Silica fine particles manufactured by Nippon Shokubai Co., Ltd.) 10 parts dispersion <Formation of photothermal conversion layer>
As described above, on the surface opposite to the back coat layer of the 75 μm-thick PET support on which the back coat layer was applied, the photothermal conversion layer coating solution was applied with a wire bar, and then in an oven at 120 ° C. It dried for minutes and formed the photothermal conversion layer on this support body. When the optical density of the obtained photothermal conversion layer at a wavelength of 808 nm was measured with a UV-spectrophotometer UV-240 manufactured by Shimadzu Corporation, OD = 1.03, and the layer thickness averaged 0.3 μm.

<Preparation of coating liquid 1 for black ink layer>
Each of the following components was put into a kneader mill, a shearing force was applied while adding a small amount of solvent, and a dispersion pretreatment was performed. A solvent was further added to the dispersion to prepare a final composition having the following composition, and sand mill dispersion was performed for 2 hours to obtain a pigment dispersion mother liquor.
[Black pigment dispersion mother liquor composition]
(Composition 1)
Polyvinyl butyral (ESREC B BL-SH: manufactured by Sekisui Chemical Co., Ltd.) 12.6 parts Carbon black (Mitsubishi Carbon Black # 5: manufactured by Mitsubishi Chemical Corporation) 4.5 parts Dispersing aid (Solsperse S-20000: manufactured by ICI) 0.8 part propyl alcohol 79.4 parts (composition 2)
Polyvinyl butyral (ESREC B BL-SH: supra) 12.6 parts Carbon black (Mitsubishi Carbon Black MA100: manufactured by Mitsubishi Chemical Corporation) 10.5 parts Dispersing aid (Solsperse S-20000: supra) 0.8 parts Propyl Next, the following components were mixed while stirring with a stirrer to prepare a black ink layer coating solution.
(Black ink layer coating solution 1)
Black pigment dispersion mother liquor (Composition 1: Composition 2 = 70: 30 parts) 185.7 parts Polyvinyl butyral (Eslec B BL-SH: supra) 11.9 parts Wax compound Stearic acid amide (Neutron 2: Nippon Seiki) 1.7 parts behenamide (diamond BM: manufactured by Nippon Kasei Co., Ltd.) 1.7 parts lauric acid amide (diamond Y: manufactured by Nippon Kasei Co., Ltd.) 1.7 parts palmitic acid amide (diamond KP: Nippon Kasei Co., Ltd.) 1.7 parts erucic acid amide (Diamid L-200: manufactured by Nippon Kasei Co., Ltd.) 1.7 parts Oleic acid amide (Diamid O-200: manufactured by Nippon Kasei Co., Ltd.) 1.7 parts Rosin ester ( KE-311: manufactured by Arakawa Chemical Co., Ltd.) 11.4 parts Fluorosurfactant (compound described in Table 1) 1.5 parts Inorganic pigment (MEK-ST, 30% MEK solution: Nissan) 7.1 parts propyl alcohol 1050 parts methyl ethyl ketone 295 parts When the particles in the obtained coating liquid 1 for black ink layer were measured using a laser scattering type particle size distribution measuring device, the average particle diameter was 0. The ratio of particles of 1 μm or more was 0.5%.

<Formation of black ink layer>
After coating the black ink layer coating solution on the surface of the light-to-heat conversion layer with a wire bar, the coated material is dried in an oven at 100 ° C. for 2 minutes to form a black ink layer on the light-to-heat conversion layer. did. When the optical density (optical density: OD) of the ink layer was measured with a Macbeth densitometer “TD-904” (W filter), OD = 0.91. Further, when the film thickness of the ink layer was measured, it was 0.60 μm on average.

  As for the physical properties of the obtained ink layer, the surface hardness is 200 g or more with a sapphire needle, the surface smoother value is 1.24 kPa at 23 ° C. and 55% RH (relative humidity), and the surface static friction coefficient is 0.08.

  Through the above steps, a black ink sheet 1 in which the photothermal conversion layer and the black ink layer were provided in this order on the support was obtained.

<Preparation of Yellow Ink Sheet 1>
In the preparation of the black ink sheet 1, the yellow ink sheet 1 was prepared in the same manner as the black ink sheet 1 except that the yellow ink layer coating liquid 1 having the following composition was used instead of the black ink layer coating liquid 1. Was made. The film thickness of the ink layer of the obtained yellow ink sheet 1 was 0.42 μm.
[Yellow pigment dispersion mother liquor]
(Composition 1)
Polyvinyl butyral (ESREC B BL-1SH: supra) 7.1 parts Yellow pigment (Novo Palm Yellow P-HG: manufactured by Clariant Japan)
12.9 parts Dispersing aid (Solsperse S-20000: supra) 0.6 parts Propyl alcohol 79.4 parts (Composition 2)
Polyvinyl butyral (ESREC B BL-1SH: supra) 7.1 parts Yellow pigment (Novo Palm Yellow M2R 70: manufactured by Clariant Japan)
12.9 parts Dispersing aid (Solsperse S-20000: supra) 0.6 parts 79.4 parts propyl alcohol (coating solution 1 for yellow ink layer)
Yellow pigment dispersion mother liquor (Composition 1: Composition 2 = 95: 5 parts) 126 parts Polyvinyl butyral (ESREC B BL-SH: supra) 4.6 parts Wax compound Stearic acid amide (Neutron 2: Nippon Seika Co., Ltd.) 1.7 parts behenamide (diamond BM: manufactured by Nippon Kasei Co., Ltd.) 1.7 parts lauric acid amide (diamond Y: manufactured by Nippon Kasei Co., Ltd.) 1.7 parts palmitic acid amide (diamond KP: Nippon Kasei) 1.7 parts erucamide (Diamid L-200: manufactured by Nippon Kasei Co., Ltd.) 1.7 parts oleic acid amide (Diamid O-200: manufactured by Nippon Kasei Co., Ltd.) 1.7 parts Rosin ester (KE-) 311: supra) 2.4 parts nonionic surfactant (chemistat 1100: manufactured by Sanyo Chemical Industries) 0.4 part fluorine-based surfactant (compound described in Table 1) 0.2 Propyl alcohol 793 parts Methyl ethyl ketone 198 parts The physical properties of the obtained ink layer are as follows. The surface hardness is 200 g or more with a sapphire needle, the surface smoother value is 310 Pa at 23 ° C./55% RH, and the surface static friction coefficient is 0.1. Met.

<Preparation of magenta ink sheet 1>
In the production of the black ink sheet 1, the magenta ink sheet 1 was prepared in the same manner as the production of the black ink sheet 1 except that the magenta ink layer coating liquid 1 having the following composition was used instead of the black ink layer coating liquid 1. Was made. The film thickness of the ink layer of the obtained magenta ink sheet 1 was 0.38 μm.
[Magenta pigment dispersion mother liquor]
(Composition 1)
Polyvinyl butyral (Denka Butyral # 2000-L: manufactured by Denki Kagaku Kogyo Co., Ltd.)
12.6 parts Magenta pigment (Shimra Brilliant Carmine 2B-229: manufactured by Dainippon Ink & Chemicals, Inc.) 15.0 parts Dispersing aid (Solsperse S-20000: supra) 0.6 parts Propyl alcohol 80.4 parts (composition) 2)
Polyvinyl butyral (Denka butyral # 2000-L: supra) 12.6 parts Magenta pigment (Lionol Red GB-4290G: manufactured by Dainippon Ink & Chemicals, Inc.)
15.0 parts Dispersing aid (Solsperse S-20000: supra) 0.6 parts Propyl alcohol 79.4 parts (Coating liquid 1 for magenta ink layer)
Magenta pigment dispersion mother liquor (Composition 1: Composition 2 = 95: 5 parts) 163 parts Polyvinyl butyral (Denkabutyral # 2000-L: supra) 4.0 parts Wax compound Stearic acid amide (Neutron 2: supra) 1.0 part behenamide (diamond BM: supra) 1.0 part lauric acid amide (diamond Y: supra) 1.0 part palmitic acid amide (diamond KP: supra) 1.0 part Elca Acid amide (Diamid L-200: supra) 1.0 part Oleic acid amide (Diamid O-200: supra) 1.0 part Rosin ester (KE-311: supra) 4.6 parts Nonionic interface Activator (Chemistat 1100, supra) 0.7 part Pentaerythritol tetraacrylate (NK ester A-TMMT: Shin-Nakamura Chemical Co., Ltd.) 2.5 parts Basic surfactant (compound described in Table 1) 0.3 parts propyl alcohol 848 parts methyl ethyl ketone 246 parts The physical properties of the obtained ink layer are as follows: the surface hardness is 200 g or more with a sapphire needle, and the surface smoother value is 23 ° C. -It was 470 Pa at 55% RH, and the static friction coefficient of the surface was 0.08.

<Preparation of Cyan Ink Sheet 1>
In the preparation of the black ink sheet 1, the cyan ink sheet 1 was prepared in the same manner as the black ink sheet 1 except that the cyan ink layer coating liquid 1 having the following composition was used instead of the black ink layer coating liquid 1. Was made. The film thickness of the ink layer of the obtained cyan ink sheet 1 was 0.45 μm.
[Cyan pigment dispersion mother liquor composition]
(Composition 1)
Polyvinyl butyral (ESREC B BL-SH: supra) 12.6 parts Cyan pigment (cyanine blue 700-10FG: manufactured by Toyo Ink Manufacturing Co., Ltd.) 15.0 parts Dispersing aid (PW-36: manufactured by Enomoto Kasei Co., Ltd.) 8 parts propyl alcohol 110 parts (composition 2)
Polyvinyl butyral (ESREC B BL-SH: supra) 12.6 parts Cyan pigment (Lionol Blue 7027: manufactured by Toyo Ink Co., Ltd.) 15.0 parts Dispersing aid (PW-36: supra) 0.8 parts Propyl 110 parts of alcohol (coating solution 1 for cyan image forming layer)
Cyan pigment dispersion mother liquor (Composition 1: Composition 2 = 90: 10 parts) 118 parts Polyvinyl butyral (ESREC B BL-SH: supra) 5.2 parts Inorganic pigment (MEK-ST: supra) 1.3 parts Wax Stearic acid amide (Neutron 2: supra) 1.0 part Behenic acid amide (diamond BM: supra) 1.0 part Lauric acid amide (diamond Y: supra) 1.0 part Palmitic acid amide (Diamid KP: supra) 1.0 part Erucamide (Diamid L-200: supra) 1.0 part Oleic acid amide (Diamid O-200: supra) 1.0 part Rosin ester (KE -311: supra) 2.8 parts pentaerythritol tetraacrylate (NK ester A-TMMT: supra)
1.7 parts Fluorosurfactant (compounds listed in Table 1) 0.4 part Propyl alcohol 890 parts Methyl ethyl ketone 247 parts <Preparation of image-receiving sheet 1>
A cushion layer coating solution 1 and an image receiving layer coating solution 1 having the following composition were prepared.
(Cushion layer coating solution 1)
Vinyl chloride-vinyl acetate copolymer (MPR-TSL: manufactured by Nissin Chemical Industry Co., Ltd.) 20 parts Plasticizer (Paraplex G-40: manufactured by CP.HALL.COMPANY) 10 parts Fluorosurfactant (PF-156A) : OMNOVA) 0.5 parts Antistatic agent (SAT-5 Super (IC): Nippon Pure Chemical Industries) 0.3 parts Methyl ethyl ketone 60 parts Toluene 10 parts N, N-dimethylformamide 3 parts (Coating for image-receiving layer) Liquid 1)
Polyvinyl butyral (ESREC B BL-1: manufactured by Sekisui Chemical Co., Ltd.) 117 parts Styrene-maleic acid half ester (oxylac SH-128: manufactured by Nippon Shokubai Co., Ltd.)
63 parts Antistatic agent (Chemist 3033: Sanyo Chemical Industries) 16 parts Fluorosurfactant (PF-156A: supra) 1.2 parts Propyl alcohol 570 parts Methanol 1200 parts 1-methoxy-2-propanol 520 parts Using a narrow-width coating machine, the cushion layer coating solution 1 is applied and dried on a white PET support (Lumirror # 130E58: manufactured by Toray Industries, Inc., thickness 130 μm), and then the image receiving layer coating solution 1 is applied. -Dried. The coating amount was adjusted so that the thickness of the cushion layer after drying was about 20 μm and the thickness of the image receiving layer was about 2 μm. The white PET support is a laminate (total thickness 130 μm,) of a void-containing PET layer (thickness 116 μm, porosity 20%) and a titanium oxide-containing PET layer (thickness 7 μm, titanium oxide content 2%) provided on both sides thereof. A void-containing plastic support having a specific gravity of 0.8).

  The produced image receiving sheet 1 was wound up in a roll form and stored for 1 week at room temperature, and then used for image recording with the following laser beam.

<Image recording>
The obtained yellow ink sheet 1 (Y1), magenta ink sheet 1 (M1), cyan ink sheet 1 (C1), black ink sheet 1 (K1) and roll-shaped product of the image receiving sheet 1 are set in an exposure device, and exposure is performed. A solid image of each color alone was formed on the image receiving sheet 1 while changing the rotation amount by 10 rpm from 400 to 700 rpm. Next, the image recording surface of this image receiving sheet was laminated on the final recording medium by heating and then peeled off at the interface between the intermediate layer and the image receiving layer of the image receiving sheet to form an image on the final recording medium.

Exposure apparatus: Color Decision II EV-laser Proofer II (manufactured by Konica Minolta MG)
Image recording density: 2400 dpi (dpi is as described above)
Image recording size: 548mm x 820mm
Temperature and humidity during exposure: 25 ° C, 50% RH
Laminator: Color Decision II EV-Laminator II (manufactured by Konica Minolta MG)
Set temperature: upper roll 100 ° C, lower roll 120 ° C
Final recording medium: Tokishi double-sided art N (Mitsubishi Paper Co., Ltd.) 127.9 g / m ²
The obtained images were evaluated for the following items.

<< Sensitivity stability >>
The density of the solid image produced as described above was measured with a reflection densitometer (manufactured by Gretag: D-196), and the density of each color was Y ≧ 1.34, M ≧ 1.46, C ≧ 1.53, The highest rotation amount among the drum rotation amounts (rpm) satisfying K ≧ 1.88 was defined as the sensitivity. In addition, ink sheets Y1, M1, C1, and K1 stored in an oven at 55 ° C. for 3 days (Y1T, M1T, C1T, and K1T) for the purpose of simulating the long-term storage stability of the ink sheet by accelerated deterioration. The sensitivity was also examined in the same manner.

  The higher the rotation (low energy) side, the higher the sensitivity. The smaller the difference between before and after the oven storage, the better the storage stability.

* The same activator is used for all four colors. ** Mass ratio A: Polyimide resin (Rika Coat SN-20F: Shin Nippon Rika Co., Ltd.)
B: Polyamideimide resin (Vilomax HR-16NN: manufactured by Toyobo Co., Ltd.)
604: Acetylene glycol surfactant (Dynol 604, 5% solution: manufactured by Air Products Japan)
309: Silicone surfactant (SLYGARD309, 5% methanol solution: manufactured by Toray Dow Corning)
FT-251, FT-400S, FT-251, FT-140A, FTX-218: Neos FC-4129: 3M PF-156A, PF-136: OMNOVA Megafak F-176PF, F-177 : Manufactured by Dainippon Ink & Chemicals, Inc. It can be seen that the implementation of the present invention improves the sensitivity reduction due to long-term storage.

Example 2
<Preparation of ink sheet>
<Preparation of temporary support 1>
A release layer composition having a solid content ratio (the active ingredient ratio for a liquid one) is as follows on a PET film having a thickness of 38 μm (Mitsubishi Chemical Polyester Co., Ltd .: T100) is 9: 1 of water and i-propyl alcohol. The mixture was diluted with a mixed solvent, coated and dried with a wire bar so that the coating amount after drying was 0.3 g / m ^2, and then heat treated at 120 ° C. for 1 minute. Furthermore, curing was performed at 60 ° C. for 48 hours to prepare a temporary support 1.
(Release layer composition)
Polyvinyl alcohol (GOHSENOL EG-30: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 85 parts Cross-linking agent (Sumitex Resin M3: manufactured by Sumitomo Chemical Co., Ltd.) 9 parts Cross-linking accelerator (ACX: manufactured by Sumitomo Chemical Co., Ltd.) 1 part Polymerizable fluorine Compound (compound described in Table 2) 5 parts <Preparation of yellow ink sheet 2>
On the release layer, a yellow ink layer coating liquid 2 having the following composition was applied and dried by wire bar coating to form an ink layer having a dry weight of 0.65 g / m ² .
[Yellow pigment dispersed mother liquor composition]
Seica First Yellow H-7055 10 parts Dispersing aid (Ajisper PB822: Ajinomoto Fine Techno Co., Ltd.) 2 parts Methyl ethyl ketone 12 parts (Yellow ink layer coating solution 2)
Yellow pigment dispersion mother liquor 18.3 parts Styrene resin (Hymer ST-95: Sanyo Chemical Industries, Ltd.) 5.0 parts Acrylic resin (Dianar BR-102: Mitsubishi Rayon Co., Ltd.) 0.4 parts Styrene-butadiene block Polymer (Kraton D-1101CU: manufactured by Shell Japan Co., Ltd.) 0.2 part Fluorosurfactant (compound described in Table 2) 0.1 part Methyl ethyl ketone 11.5 parts Cyclohexanone 64.5 parts On the yellow ink layer The photothermal conversion layer coating solution 2 having the following composition was applied and dried by wire bar coating to form a photothermal conversion layer having a drying weight of 0.73 g / m ² .
(Photothermal conversion layer coating solution 2)
Polyvinyl alcohol (GOHSENOL EG-30: supra) 3.8 parts Carbon black aqueous dispersion (CAB-O-JET300: manufactured by CABOT)
13.3 parts Boric acid 0.2 parts Fluorosurfactant (FT-251: Neos) 0.1 part Pure water 63.7 parts i-propyl alcohol 18.9 parts On the other hand, a transparent PET (thickness 75 μm) T100, # 75: manufactured by Mitsubishi Chemical Polyester Co., Ltd.), a backcoat layer coating solution having the following composition was applied by wire bar coating to form a backcoat layer having a dry weight of 0.65 g / m ² .
(Backcoat layer coating solution)
Polyvinyl alcohol (GOHSENOL EG-05: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 4.7 parts Antistatic agent (Efcol 214: manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) 1.5 parts Matt material (PMMA particles having a volume average particle size of 5.6 μm) 57 parts aqueous solution) 0.6 parts Fluorine-based resin aqueous solution (Unidyne TG-470B: manufactured by Daikin Industries, Ltd.) 0.9 parts Fluorine-based surfactant (FT-251: manufactured by Neos) 0.1 parts Pure water 81.7 Part i-Propyl alcohol 9.5 parts A cushion layer coating solution having the following composition was applied to the opposite surface of the back coat layer by wire bar coating to form a cushion layer having a dry weight of 7 g / m ² .
(Cushion layer coating solution)
Styrene-ethylene-butylene block copolymer (Kraton G1657: manufactured by Shell Japan) 10.0 parts Tackfire (Superester A100: manufactured by Arakawa Chemical Industries) 4.3 parts Methyl ethyl ketone 17.1 parts Toluene 68.6 parts Next, after the photothermal conversion layer side of the temporary support 1 provided with the yellow ink layer and the photothermal conversion layer is opposed to the cushion layer and bonded together by roll touch, the temporary support with a release layer is provided. 1 was peeled off to obtain a yellow ink sheet 2.

<Preparation of magenta ink sheet 2>
A magenta ink sheet 2 was obtained in the same manner as the yellow ink sheet 2 except that the yellow ink layer coating liquid 2 was replaced with a magenta ink layer coating liquid 2 having the following composition. The dry weight of the magenta ink layer was 0.67 g / m ² .
[Magenta pigment dispersion mother liquor composition]
Brilliant Carmine 6B 15 parts Dispersing aid (Ajisper PB822: Ajinomoto Fine Techno Co., Ltd.) 4.5 parts Methyl ethyl ketone 80.5 parts (Magenta ink layer coating solution 2)
Magenta pigment dispersion mother liquor 13.9 parts Styrene resin (Heimer ST-95: supra) 4.6 parts Acrylic resin (Dianar BR-102: supra) 0.4 part Styrene-butadiene block copolymer (Kraton D) -1101CU: The above)
0.3 part Fluorine-based surfactant (compound described in Table 2) 0.1 part Methyl ethyl ketone 16.4 parts Cyclohexanone 64.3 parts <Preparation of cyan ink sheet 2>
A cyan ink sheet 2 was obtained in the same manner as the yellow ink sheet 2 except that the yellow ink layer coating liquid 2 was replaced with the cyan ink layer coating liquid 2 having the following composition. The dry weight of the cyan ink layer was 0.70 g / m ² .
[Cyan pigment dispersion mother liquor composition]
Phthalocyanine blue (PB15: 3) 30 parts Dispersing aid (Solsperse 24000: manufactured by ICI) 5 parts Methyl ethyl ketone 65 parts (Cyan ink layer coating solution 2)
Cyan pigment dispersion mother liquor 5.2 parts Styrene resin (Heimer ST-95: supra) 5.7 parts Acrylic resin (Dianal BR-102: supra) 0.4 part Styrene-butadiene block copolymer (Kraton D) -1101CU: The above)
0.3 part Fluorine-based surfactant (compound described in Table 2) 0.1 part Methyl ethyl ketone 24.1 parts Cyclohexanone 64.2 parts <Preparation of black ink sheet 2>
The yellow ink sheet 2 was replaced with the black ink layer coating liquid 2 having the following composition, and the photothermal conversion layer coating liquid 2 was replaced with the photothermal conversion layer coating liquid 3 having the following composition. Thus, a black ink sheet 2 was obtained. The dry weight of the black ink layer was 0.87 g / m ² , and the dry weight of the photothermal conversion layer was 0.73 g / m ² .
[Black pigment dispersion mother liquor composition]
Carbon black 25 parts Dispersing aid (Solsperse 24000: manufactured by ICI) 5 parts Methyl ethyl ketone 70 parts [Violet pigment dispersion mother liquor composition]
Dioxazine violet 10 parts Dispersing aid (Solsperse 24000: supra) 5 parts Methyl ethyl ketone 85 parts (Black ink layer coating solution 2)
The above black pigment dispersion mother liquor 8.0 parts The above violet pigment dispersion 1.4 parts Cyan pigment dispersion mother liquor (supra) 1.1 parts Styrene resin (Heimer ST-95: supra) 6.2 parts Acrylic resin (Dianal) BR-85: manufactured by Mitsubishi Rayon Co., Ltd.) 1.1 parts Styrene-isoprene block copolymer (Kraton D-1117P: manufactured by Shell Japan) 0.2 parts Fluorine-based surfactant (compound described in Table 2) 0.1 Parts methyl ethyl ketone 19.2 parts cyclohexanone 62.7 parts (photothermal conversion layer coating solution 3)
Polyvinyl alcohol (GOHSENOL EG-30: supra) 3.7 parts Carbon black aqueous dispersion (CAB-O-JET300: supra) 14.3 parts boric acid 0.2 part Fluorosurfactant (FT-251: supra) Out) 0.1 part Pure water 62.9 parts i-Propyl alcohol 18.8 parts <Preparation of white ink sheet>
A white ink sheet 1 was obtained in the same manner as the yellow ink sheet 2 except that the yellow ink layer coating liquid 2 was replaced with the white ink layer coating liquid 1 having the following composition. The dry weight of the white ink layer was 2.0 g / m ² .
[White pigment dispersion mother liquor composition]
White pigment (titanium oxide, specific gravity 4.1) 60.0 parts Dispersion aid (Solsperse 5000: manufactured by ICI) 1.0 part Dispersion aid (Solsperse 24000: supra) 5.0 parts Methyl ethyl ketone 34.0 parts ( White ink layer coating liquid)
125 parts of the above-mentioned white pigment dispersion mother liquor Styrene resin (Himmer ST-95: supra) 12.3 parts PMMA resin (Dianal BR85: supra) 5.0 parts Fluorosurfactant (compound described in Table 2) 0. 2 parts Methyl ethyl ketone 224 parts Cyclohexanone 630 parts The average dispersed particle size of the pigment contained in the white ink layer coating solution was 250 nm. The transmission density of the white ink layer (yellow density measured with a Macbeth TD904 densitometer) was 0.29.

<Preparation of image receiving sheet 2>
Using a white PET (U51L74: manufactured by Teijin) with a thickness of 100 μm as a support, a backcoat layer coating solution having the following composition is applied by wire bar coating to form a backcoat layer with a dry weight of 2.3 g / m ^2. did.
(Backcoat layer coating solution)
Polyester resin (Byron 200: manufactured by Toyobo Co., Ltd.) 11.5 parts Black pigment dispersion (MHI Black # 273: manufactured by Gokoku Color Co., Ltd.) 6.6 parts Polyester-modified silicone (X-24-8300: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 part PMMA particles (MX-1000: manufactured by Soken Chemical Co., Ltd.) 0.4 part Methyl ethyl ketone 21.0 parts Toluene 20.0 parts Cyclohexanone 40.0 parts On the opposite surface of the back coat layer, a cushion layer having the following composition was applied. Liquid 2 was applied by wire bar coating to form a cushion layer having a dry weight of 17.5 g / m ² .
(Cushion layer coating solution 2)
Polyethylene latex (Hitech S-3127: manufactured by Toho Chemical Industry Co., Ltd.) 94.3 parts Pure water 5.7 parts On the cushion layer, an intermediate layer coating solution having the following composition was applied by wire bar coating, and the dry weight was 3. An intermediate layer of 0 g / m ² was formed.
(Interlayer coating solution)
Ethylcellulose (STD10 (PREM): Dow Chemical Co., Ltd.) 9.5 parts Methanol-modified ethanol 90.5 parts On the intermediate layer, an image-receiving layer coating solution 2 having the following composition is applied by wire bar coating, and the dry weight is applied. An image receiving layer of 1.35 g / m ² was formed.
(Image-receiving layer coating solution 2)
Acrylic resin (Iodosol AD-133: manufactured by NSC Japan) 22.0 parts Fluororesin (Unidyne TG-472A: manufactured by Daikin Industries) 4.4 parts PMMA particles (MX40S-2: manufactured by Soken Chemical Co., Ltd.) 2.1 parts Pure water 62.8 parts i-propyl alcohol 8.7 parts <Image recording>
The yellow ink sheet 2 (Y2), the magenta ink sheet 2 (M2), the cyan ink sheet 2 (C2), the black ink sheet 2 (K2), and the white ink sheet (W) are used as the ink sheets, and the image receiving sheet 2 is used as the image receiving sheet. Image recording was performed in the same manner as in Example 1 except that was used. However, for the white ink sheet, the final recording medium was a transparent PET film having a thickness of 100 μm (Lumirror 100U-94: manufactured by Toray Industries, Inc.).

  The obtained images were evaluated for the following items.

<< Sensitivity stability >>
The density of the solid image produced in the same manner as in Example 1 was measured with a reflection densitometer D-196 (supra), and the density of each color was Y ≧ 1.34, M ≧ 1.46, C ≧ 1.53, The highest rotation amount among the drum rotation amounts for which K ≧ 1.88 was taken as the sensitivity. Only the white ink sheet was measured with a transmission densitometer (manufactured by Macbeth: TD-904), and the highest rotation amount among drum rotation amounts satisfying W ≧ 0.29 (blue filter) was defined as the sensitivity.

  In addition, as in Example 1, ink sheets Y2, M2, C2, K2, and W were stored in an oven at 55 ° C. for 3 days (Y2T, M2T, C2T, K2T, and WT), and the sensitivity was examined. It was.

《50% dot gain fluctuation amount》
Using the same exposure apparatus and laminator as in Example 1, image exposure was performed in the order of white, black, cyan, magenta, and yellow under the following conditions to form a five-color image on the image receiving sheet. Subsequently, the image recording surface of this image receiving sheet is laminated on the following final recording medium by heat lamination, and then peeled off at the interface between the intermediate layer and the image receiving layer of the image receiving sheet, and a proof image having a multicolor transfer image on the final recording medium Got.

  Using a Digital Microscope DMS910 (manufactured by TECHKON), the dot gain amount at the halftone dot portion of each monochromatic color of the obtained image was measured, and the dot gain (DG) fluctuation amount was determined by the following equation. For white, an image formed on Lumirror 100U-94 was used, and the dot gain amount was measured after black backing.

Image exposure energy: 230 mJ / cm ²
Image recording density: 2400 dpi (dpi is as described above)
Image recording size: 548mm x 820mm
Image content: ISO / JIS-SCID standard image N1 (portrait)
Exposure temperature and humidity: 25 ℃ ・ 50% RH and 18 ℃ ・ 30% RH
Final recording medium: Tokuhishi double-sided art N (Mitsubishi Paper Industries) 127.9 g / m ² and Lumirror 100U-94 (Toray Industries, Inc.) 100 μm
DG fluctuation amount = (dot gain amount at 25 ° C./50% RH exposure) − (dot gain amount at 18 ° C./30% RH exposure)
<< Reproducibility of fine lines >>
For an image exposed at 18 ° C. and 30% RH, the 10 μm fine line reproducibility of each single color was evaluated in three stages according to the following criteria.

○: The thin line is deficient and there is no “garbage” △: A part of the thin line is deficient ×: More than half of the fine line is deficient

* Use the same activator for all five colors ** Mass ratio C: Unidyne TG-470B (Daikin Industries)
D: Unidyne TG-472A (manufactured by Daikin Industries)
604: Acetylene glycol surfactant (Dynol 604, 5% solution: manufactured by Air Products Japan)
309: Silicone surfactant (SLYGARD309, 5% methanol solution: manufactured by Toray Dow Corning)
FT-250, FT-251, FT-140A, FTX-218, FT-400S: Neos FC-4129: 3M PF-136A, PF-156: OMNOVA Megamega F-178K: Dainippon Ink Made by Chemical Industry Co., Ltd. By carrying out the present invention, it can be seen that both the sensitivity decrease during storage and the fluctuation of 50% DG due to temperature and humidity are small, and the fine line reproducibility is excellent.

Example 3
<Preparation of ink sheet>
<Preparation of temporary support 2>
A 38 μm thick PET film (T100: mentioned above) is diluted with a 9: 1 mixed solvent of water and i-propyl alcohol with a solid content ratio (the active ingredient ratio is the liquid one) as follows. After coating and drying with a wire bar so that the subsequent coating amount was 0.3 g / m ² , heat treatment was performed at 120 ° C. for 1 minute. Furthermore, curing was performed at 60 ° C. for 48 hours to prepare a temporary support 2.
(Release layer composition)
Polyvinyl alcohol (GOHSENOL EG-30: supra) 85 parts Cross-linking agent (Smitex Resin M3: supra) 9 parts Cross-linking accelerator (ACX: supra) 1 part Polymerizable fluorine compound (thing described in Table 3) 5 parts <Preparation of Yellow Ink Sheet 3>
On the release layer, a yellow ink layer coating solution 3 having the following composition was applied and dried by wire bar coating to form an ink layer having a dry weight of 0.65 g / m ² .
(Yellow ink layer coating solution 3)
Yellow pigment dispersion (MHI Yellow # 625: Gokoku Color Co., Ltd., 10% solid content)
19.0 parts Styrene-acrylic resin (Hymer SBM73F: Sanyo Chemical Industries) 2.4 parts Ethylene-vinyl acetate resin (EV-40Y: Mitsui DuPont Polychemicals)
0.2 parts Fluorine-based surfactant (compounds listed in Table 3) 0.1 part Methyl ethyl ketone 48.1 parts Cyclohexanone 30.4 parts On the yellow ink layer, a photothermal conversion layer coating solution 4 having the following composition was added to the wire bar. It was applied and dried by coating to form a photothermal conversion layer having a drying weight of 0.70 g / m ² .
(Photothermal conversion layer coating solution 4)
Polyvinyl alcohol (Gosenol EG-30: supra) 0.7 part Carbon black dispersion (SD-9020: manufactured by Dainippon Ink and Co., 40% solid content)
0.9 part fluorine-based surfactant (FT-251: supra) 0.1 part pure water 6.6 parts i-propyl alcohol 1.8 parts Photothermal conversion layer of the above coating and the same support as in Example 2 After the body, the back coat layer, and the cushion layer applied to the cushion layer were bonded together by roll touch, the temporary support 2 with a release layer was peeled off to obtain a yellow ink sheet 3.

<Preparation of magenta ink sheet 3>
A magenta ink sheet 3 was obtained in the same manner as the yellow ink sheet 3 except that the yellow ink layer coating liquid 3 was replaced with a magenta ink layer coating liquid 3 having the following composition. The dry weight of the magenta ink layer was 0.67 g / m ² .
(Magenta ink layer coating solution 3)
Magenta pigment dispersion (MHI magenta # 1038, manufactured by Mikuni Color Co., Ltd., solid content 19.5%
) 12 parts Styrene-acrylic resin (Hymer SBM73F: supra) 2.4 parts Ethylene-vinyl acetate resin (EV-40Y: supra) 0.2 parts Fluorosurfactant (compound described in Table 3) 0.1 Methyl ethyl ketone 60.5 parts Cyclohexanone 24.8 parts (Preparation of cyan ink sheet 3)
A cyan ink sheet 3 was obtained in the same manner as the yellow ink sheet 3 except that the yellow ink layer coating liquid 3 was replaced with the cyan ink layer coating liquid 3 having the following composition. The dry weight of the cyan ink layer was 0.67 g / m ² .
(Cyan ink layer coating solution 3)
Cyan pigment dispersion (MHI cyan # 454: manufactured by Mikuni Dye Co., Ltd., solid content 35%) 5.1 parts Styrene-acrylic resin (Himmer SBM73F: supra) 2.9 parts Ethylene-vinyl acetate resin (EV-40Y: front Out) 0.2 parts Fluorosurfactant (compounds listed in Table 3) 0.1 part Methyl ethyl ketone 50.3 parts Cyclohexanone 42 parts <Preparation of black ink sheet 3>
The same procedure as in the preparation of the yellow ink sheet 3 was performed except that the yellow ink layer coating liquid 3 was replaced with the black ink layer coating liquid 3 having the following composition and the photothermal conversion layer coating liquid 4 was replaced with the photothermal conversion layer coating liquid 5 having the following composition. Thus, a black ink sheet 3 was obtained. The dry weight of the black ink layer was 0.67 g / m ² , and the dry weight of the photothermal conversion layer was 0.73 g / m ² .
(Black ink layer coating solution 3)
Black pigment dispersion (MHI Black # 220: Gokoku Color Co., Ltd., solid content: 39.6%)
4.9 parts Cyan Pigment Dispersion (MHI Cyan # 454: supra) 0.9 Part Violet Pigment Dispersion (MHI Violet # 735: Migoku Dye Co., solid content 15
1.2) Styrene-acrylic resin (Hymer SBM73F: supra) 3.9 parts Ethylene-vinyl acetate resin (EV-40Y: supra) 0.3 part Fluorosurfactant (compound described in Table 3) 0.1 part methyl ethyl ketone 57.9 parts cyclohexanone 30.8 parts (photothermal conversion layer coating solution 5)
46.7 parts of a 10% aqueous solution of polyvinyl alcohol (Gosenol EG-30: supra) Carbon black dispersion (SD-9020: manufactured by Dainippon Ink Co., Ltd., solid content 40%)
6.4 parts Fluorosurfactant (FT-251: supra) 0.1 part Pure water 28.2 parts i-Propyl alcohol 18.6 parts <Preparation of image receiving sheet 3>
An image receiving sheet 3 was produced in the same manner as in Example 2 except that the support used in Example 2 was replaced with transparent PET (T-100: manufactured by Mitsubishi Chemical Polyester) having a thickness of 100 μm.

<Image recording>
The obtained yellow ink sheet 3 (Y3), magenta ink sheet 3 (M3), cyan ink sheet 3 (C3), black ink sheet 3 (K3), and roll-shaped product of the image receiving sheet 3 are set in the following exposure apparatus, A solid image and a fine line pattern of each color alone were formed on the image receiving sheet 3 while changing the exposure rotation amount by 10 rpm from 400 to 600 rpm. Next, the image recording surface of this image receiving sheet was laminated on the final recording medium by heating and then peeled off at the interface between the intermediate layer and the image receiving layer of the image receiving sheet to form an image on the final recording medium.

Exposure apparatus: Color Decision I EV-laser Proofer (manufactured by Konica Minolta MG)
Image recording density: 4000 dpi (dpi is as described above)
Image recording size: 514mm x 625mm
Exposure temperature and humidity: 23 ° C, 50% RH
Laminator: Color Decision EV-Laminator (manufactured by Konica Minolta MG)
Set temperature: Heat roller 130 ° C, drum 100 ° C
Final recording medium: Tokishi double-sided art N (Mitsubishi Paper Co., Ltd.) 127.9 g / m ²
The obtained images were evaluated for the following items.

<Sensitivity stability>
The density of the solid image produced in the same manner as in Example 1 was measured with a reflection densitometer D-186 (supra), and the density of each color was Y ≧ 1.34, M ≧ 1.46, C ≧ 1.53, The highest rotation amount among the drum rotation amounts satisfying K ≧ 1.78 was defined as the sensitivity.

  Similarly to Example 1, ink sheets Y3, M3, C3, and K3 stored in an oven at 55 ° C. for 3 days (Y3T, M3T, C3T, K3T) were prepared, and the sensitivity was examined.

<< Reproducibility of fine lines >>
Among the images formed by Y3T, M3T, C3T, and K3T, the 12 μm fine line reproducibility of each single color was evaluated in three stages according to the following criteria.

○: The thin line is deficient and there is no “garbage” △: A part of the thin line is deficient ×: More than half of the fine line is deficient

* Use the same activator for all four colors ** Mass ratio C: Unidyne TG-470B (Daikin Industries)
D: Unidyne TG-472A (manufactured by Daikin Industries)
604: Acetylene glycol surfactant (Dynol 604, 5% solution: manufactured by Air Products Japan)
309: Silicone surfactant (SLYGARD309, 5% methanol solution: manufactured by Toray Dow Corning)
FT-250, FT-251, FT-140A, FTX-218, FT-400S: Neos FC-4129: 3M PF-136A, PF-156: OMNOVA Megamega F-178K: Dainippon Ink Made by Chemical Industry Co., Ltd. By carrying out the present invention, it can be seen that there is little decrease in sensitivity during storage and excellent thin line reproducibility.

Claims (10)

Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In an image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, the ink layer is branched into molecules. An ink sheet comprising a surfactant having a fluoroalkyl group. Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In an image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, two ink layers are contained in the molecule. An ink sheet comprising a surfactant having the above perfluoroalkyl group. Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In the image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, the ink layer has 1 to 6 carbon atoms. An ink sheet comprising a surfactant having a perfluoroalkyl group. Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In an image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, the ink layer has the following general formula (1) An ink sheet comprising at least one surfactant represented by (7) to (7).
The general formula ₍₁₎ Rf 1 -OR 1
Formula _{(2) Rf 1 -O-L} -Rf 1

In the general formulas (1) to (4), Rf ₁ represents a [(CF ₃ ) ₂ C] ₂ C═C (CF ₃ ) — group or a (CF ₃ ) ₂ C═C (C ₂ F ₅ ) — group. L represents a linking group, and R ₁ represents a polar group. a, b, c, d, e, f and g each represent an integer of 1 to 40.

In Formula (5) ~ (7), Rf 2 represents a perfluoroalkyl group having 1 to 7 carbon atoms, R ₂ represents a polar group. m1, m2, m3 and n1 each represents an integer of 1 to 40. Using an image receiving sheet having at least an image receiving layer on a support and a plurality of ink sheets having at least a light-to-heat conversion layer and an ink layer on the support, the ink layer of each ink sheet and the image receiving layer of the image receiving sheet are opposed to each other. In an image forming material for recording an image by irradiating laser light from the ink sheet side and transferring the laser light irradiation area of the ink layer onto the image receiving layer of the image receiving sheet, the ink layer has the following general formula (8) An ink sheet comprising at least one of an acetylene glycol-based surfactant or a silicone-based surfactant represented by

In the formula, each of R ^{1 to} R ⁴ represents a hydrogen atom, a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. , EO represents an ethyleneoxy group which may be substituted, and m and n each represent an integer of 0-50. The ink sheet according to claim 1, wherein the ink layer is at least four types of yellow, magenta, cyan, black, and white. After pasting the cushion layer surface and the light-to-heat conversion layer surface of the temporary support on which the release layer, the ink layer, and the light-to-heat conversion layer are coated in this order, and the cushion layer on another support are coated The ink sheet according to any one of claims 1 to 6, wherein the ink sheet is prepared by peeling a temporary support provided with a release layer. The release layer contains at least one homopolymer or copolymer of a polymerizable fluorine compound having (perfluoroalkyl group or perfluoroalkenyl group) and (acrylic acid group or methacrylic acid group) in the molecule. The ink sheet according to claim 7. A multicolor image forming method using the image forming material according to any one of claims 1 to 8, wherein the image recording density of the irradiated laser beam is 2,000 dpi (dpi is 1 inch, that is, dots per 2.54 cm). The image forming method, wherein The image forming method according to claim 9, wherein a recording area of the multicolor image is 500 × 600 mm or more.