FR2601467A1 - IMAGE FORMING METHOD AND TRANSFER RECORDING MEDIUM USED IN THIS METHOD - Google Patents

Abstract

THE INVENTION RELATES TO A TRANSFER RECORDING MEDIA. THIS SUPPORT INCLUDES A SUBSTRATE 1B AND A LAYER 1A OF VAPORISABLE INK. LAYER 1A CAUSES A MODIFICATION OF THE VAPORIZATION DEGREE OF A COLOR CONTAINED THEREIN UNDER THE INFLUENCE OF SEVERAL KINDS OF ENERGY, FOR EXAMPLE HEAT AND LIGHT. LAYER 1A IS EXPOSED TO VARIOUS ENERGIES OF WHICH AT LEAST ONE IS APPLIED DEPENDING ON THE IMAGE TO GENERATE A VAPORIZABLE PORTION IN LAYER 1A. THE COLOR CONTAINED IN THE SPRAYABLE PORTION IS THEN TRANSFERRED TO A SUBSTRATE SUCH AS PLAIN PAPER. PROVIDING MULTIPLE KINDS OF ENERGY MAKES A HIGH QUALITY COLOR TRANSFER IMAGE EASIER IN A COMPACT APPARATUS BY THE FUNCTIONAL SEPARATION OF TRAINING AND IMAGE TRANSFER OPERATIONS. THE TRANSFER RECORDING MEDIA MAY BE USED MULTIPLE TIMES.

Description

The present invention relates to an image forming method and a

  transfer recording medium, usable for printers,

  copiers and copying machines in facsimile.

  In recent years, in response to the increasing demand for recording processes adapted to various information processing systems, the thermal or heat-sensitive recording technique has attracted much attention, and research and related development

  to this technique have been actively accomplished.

  However, the thermal transfer recording method of the prior art is not devoid of drawbacks. Examples of some of them are mentioned below.

  (1) Since a transfer recording medium used in conventional recording methods can not be used more than once, the cost of sacrificed supplies has been high. In addition, to obtain an image in several colors, it was

  necessary to use a thermal transfer recording medium for each of the different colors.

  In this case, the cost mentioned above was still

bigger.

  (2) - Because thermal conduction has a low response rate compared to electricity or light, it has generally been difficult to adjust a heat pulse so that a medium shade can be reproduced with the conventional recording system using a

  thermal head, and it was also impossible to perform a recording in medium shade, since the layer of photosensitive transfer ink does not assume a transfer function for a gradient representation.

  (3) In the conventional thermal transfer recording method, it has been possible to obtain only one image color in a transfer operation, and as a result it has been necessary to repeat several times the transfer to superimpose colors in order to obtain a multicolored image.

  It is very difficult to exactly superimpose images of different colors, so that it has been difficult to obtain an image without chroma or deviation. In particular, when observing an element

  image, it is found that the color superposition has hardly been performed in such an element, and accordingly, a multicolor image has been constituted by the assembly or grouping of image elements involving a color difference in the conventional thermal transfer recording method. For this reason, it has not been possible to obtain a clear multicolor image in accordance with the conventional thermal transfer recording method.

  It has further been proposed a transfer image formation method for the production of a multicolored image by the use of a color precursor (color material) and a developer (United States patent). America No. 4,399,209). More particularly, in this method, there is provided an image forming sheet comprising a substrate having a layer of a chromogenic material and a radio-curable composition encapsulated in rupturable capsules; the coating is exposed for actinic radiation imaging to cure the radiation curable composition and form a latent image; and the latent image is superimposed on a sheet comprising a developer layer to form a visible image on that sheet. In such a known method, light energy alone is used to form a latent image on a transfer recording medium (image sheet), so that a recording medium of high sensitivity to light or at a luminous flux, or that a high energy is needed in order to obtain a sharp, high-speed image. In general, a high sensitivity recording medium has low storage stability and therefore is not amenable to easy handling. Furthermore, it is difficult to obtain the high energy required for the hardening of a radio-curable composition at a high speed with only one type of energy, especially light energy, which is why it has generally been resorted to a device

large dimensions.

  In order to solve the mentioned problems

  above, the Applicant's research group has proposed an image forming method (U.S. Patent Application No. 869,689 corresponding to Japanese Patent Application No. 128814/1986).

  The subject of these patent applications is based on an image forming method, which consists of: taking a transfer recording medium comprising a transfer recording layer, which is capable of causing irreversible change in its transfer characteristic under the effect of several types of energy; exposing to the various types of energy the transfer recording layer under selected conditions so that at least one of the various types of energy corresponds to a recording information signal so as to form a transferable portion in the transfer recording layer; and transferring the transferring portion of the transfer recording layer to a transfer receiving medium thereby leaving an image corresponding to the transferable portion on the transfer medium;

support receiving the transfer.

  The main object of the present invention is, therefore, to find a training method

  image which solves the aforementioned problems accompanying the conventional method of thermal transfer recording and which provides an improvement to the aforementioned image forming method previously proposed by the research group of the Applicant.

  A particular object of the present invention is to provide an image forming method by which a high quality multicolor transfer image can be easily obtained, and in which a transfer recording medium can be used.

several times.

  Another object of the present invention is to find a trans-recording medium that can be used in the training process.

picture above.

  According to the present invention,

  there is provided a transfer recording medium comprising a substrate on which is disposed a vaporizable ink layer, the vaporizable ink layer containing a vaporizable dye and being capable of modifying the vaporization degree of the vaporizable dye under the vaporizable ink layer. effect of several types of energy.

  In accordance with the present invention, there is also provided an image forming method, which comprises: taking the transfer recording medium mentioned above; exposing the vaporizable ink layer to the various types of energy under conditions such that at least one of the various types of energy corresponds to a recording information signal, thereby forming a vaporizable portion in the vaporizable ink layer; and vaporizing the vaporizable dye in the vaporizable ink layer so as to transfer the vaporizable dye to a transfer receiving medium thereby forming an image corresponding to the vaporizable portion on the transfer receiving medium. In accordance with another aspect of the present invention, there is provided a transfer recording medium comprising a substrate having a vaporizable ink layer, which comprises a distributed layer of imaging elements capable of providing several colors, each imaging element containing a vaporizable dye capable of producing one of the various colors, each imaging element being capable of modifying the vaporization degree of the vaporizable dye when exposed to various types of energy in a

  a particular energy condition depending on the color of the vaporizable dye contained therein.

  In accordance with the present invention, there is also provided an image forming method, which comprises: taking the transfer recording medium mentioned above; exposing to the various types of energy the vaporizable ink layer under energetic conditions which correspond, respectively, to the various colors, and to a recording information signal, so as to thereby form a vaporizable portion in the layer vaporizable ink; and

  vaporizing the vaporizable dye in the vaporizable ink layer to transfer the vaporizable dye to a transfer-receiving medium to form an image corresponding to the vaporizable portion on the transfer-receiving medium.

  The term "vaporizable portion" as used herein means a portion of the vaporizable ink layer created by a local variation in the degree of vaporization or vaporization ability. The vaporizable portion is generally

  by clearly visible, but it can be visible.

  In addition, the color of the aforementioned image formed on the carrier receiving the transfer may be different from a color of the vaporizable dye disposed on the transfer recording medium. As a result, the vaporizable dye may be colorless when placed on the support

transfer recording.

  Other features and benefits

  of the present invention will emerge from the detailed description which follows, made with reference to the drawings

attached.

  The term "parts" and the symbol "%" used hereinafter in the case of a composition are by weight unless otherwise specified.

  Figs. 1A-1C are schematic partial sectional representations showing the relationship between a trans recording medium and a thermal head involved in a multi-color transfer recording mode in accordance with the present invention; Fig. 2 is a schematic side view showing an example of a device 35 for carrying out the image forming method according to the present invention; Figures 3, 5 and 6 are respective timing diagrams of the time of action of the energy sources used in one embodiment of the image forming method according to the present invention; and

  Fig. 4 is a graphical representation of a relationship between an image density and a duration T (under the action of light energy only).

  The thermal recording medium according to the present invention comprises a substrate having a vaporizable ink layer thereon, and can provide an image on a transfer receiving medium (or a recording medium) by vaporization of a vaporizable dye contained in

the vaporizable ink layer.

  More particularly, when several types of energy are caused to act on the vaporizable ink layer, a portion is formed in which the vaporizable dye can be substantially vaporized (i.e., a vaporizable portion) and portion in which the dye can be hardly vaporized (that is to say a non-vaporizable portion). The difference in degree of vaporization (or vaporization) of the vaporizable dye forms a latent image of recording in the vaporizable ink layer. Then, the vaporizable dye in the vaporizable portion is vaporized by imparting a transferred (or recorded) image to a transfer receiving medium. The latent registration image mentioned above is not usually clearly

visible, but may be visible.

  The degree of vaporization of the vaporizable dye, under the effect of several types of energy, can vary according to the following mechanism.

  Thus, in the vaporizable ink layer, a functional component capable of being polymerized or depolymerized is contained in addition to the vaporizable dye. When the vaporizable ink layer is exposed to several types of energy, the functional component is polymerized or depolymerized thereby influencing the vaporization degree of the vaporizable dye. For example, the vaporization of the vaporizable dye is prevented by the polymerization of the functional component, and the vaporizable dye contained in a portion in which the functional component is polymerized may be difficult to vaporize. On the contrary, in the case where the functional component is depolymerized, the vaporization of the vaporizable dye is favored. There is also another mechanism where the degree of vaporization changes because of a reaction of the vaporizable dye itself, under the effect of several types of energy. There may be, for example, the following cases: (1) a case in which the vaporizable dye, when exposed to several types of energy such as light and heat, is polymerized to form a polymer, so that that its degree of vaporization is reduced; (2) a case where the vaporizable dye, when exposed to several types of energy such as light and heat, is chemically bonded to another component, so that its degree of vaporization is reduced; etc. The expression "vaporizable dye" used

  herein means a dye such as a sublimable dye which can pass from a solid state to a vapor state or a gaseous state without passing through a liquid phase, or a dye which can pass from a solid state to a solid state. state of vapor or gaseous state in

by a liquid phase.

  FIGS. 1A-1C are partial sectional schematic representations illustrating an embodiment of the image forming method according to the present invention, which shows a relationship between a transfer recording medium of the present invention and a thermal head. An embodiment of the invention is described below wherein the degree of vaporization of the vaporizable dye is modified by polymerization or depolymerization of the functional component.

  In Fig. 1A, a vaporizable ink layer 1a is formed as a layer of small distributed imaging elements 31. Each imaging element comprises at least one vaporizable dye and a functional component, and the functional component is polymerized or depolymerized

  when exposed to several types of energy.

  The following is a description of an embodiment in which light energy

  and thermal energy represent the different

types of energy used.

  In this embodiment, a thermal energy modulated in accordance with a recording signal is exerted together with a light energy whose wavelength is chosen according to the color presented by a vaporizable dye contained in a light forming element. image which is intended to be polymerized or depolymerized. The term "modulation" here refers to an operation of changing a position in which the energy is applied according to a given image signal, and the term "jointly" covers a case where the light energy and the thermal energy are applied simultaneously as well as a case where light energy and thermal energy

are applied separately. -

  A transfer recording medium 1 according to this embodiment comprises a vaporizable ink layer 1a disposed on a substrate 1b. The vaporizable ink layer 1c consists of a layer of small, distributed imaging elements 31. The respective imaging elements contain vaporizable dyes showing, respectively, various shades of color. In the embodiment shown in FIGS. 1A-1C, for example, each imaging member 31 contains any vaporizable dye capable of being vaporized by having a selected color between cyan (C), magenta ( M) and yellow (Y). The vaporizable dyes to be contained in the imaging elements 31 are however not limited

  cyan, magenta and yellow, but may be vaporizable dyes of any color, according to a desired purpose. In addition, in the case where only one type of vaporizable dye is used, an image of a single color can be obtained.

  Each imaging element 31

  contains, in addition to the vaporizable dye, a functional or sensitive component which is polymerized or depolymerized by exposure to light energy and thermal energy.

  We will explain in detail below a case

  the degree of vaporization of the vaporizable dye contained in the imaging member 31 is reduced due to curing of the imaging member 31 under the effect of the polymerization.

  The functional component of the elements 31

  image formation has a dependence on the wavelength according to the vaporizable dye contained therein.

  More particularly, an imaging element 31 containing a vaporizable dye capable of exhibiting

260 1 46?

  In this case, a yellow color by vaporization is cured by abrupt polymerization when exposed to a heat flux and a light beam of a wavelength (Y). Also, an image forming member 31 containing a vaporizable dye capable of having a magenta color and an image forming member 31 containing a vaporizable dye, respectively, capable of having a cyan color, harden under the effect of abrupt polymerization when exposed to heat and a light beam of wavelength λ (M), and, respectively, to heat and a light beam of a wavelength At (C). An image forming member 31, once cured, is not softened even when heated during a subsequent vaporization step, so that the vaporizable colorant contained in the forming member 31 image in the cured state can not be freely vaporized. As a result, the vaporizable dye contained in the uncured imaging member 31 is selectively vaporized. Alternatively, in the case where the imaging member 31 comprises a capsule as hereinafter described, the capsule of the hardened imaging member 31 is not broken during the step subsequent vaporization, so that the vaporizable dye contained in the hardened formation element 31

  image can not be freely vaporized.

  Heat and light are applied in accordance with an information signal to be recorded. In addition, it is possible to change the degree of polymerization of a polymerizable component by varying the amount of light energy or thermal energy applied thereto. Accordingly, by adjusting the amount of light or heat energy, the degree of vaporization of the vaporizable dye can be varied in the vaporization step, so that medium-shade images having For example, the degree of polymerization of the polymerizable component can be modified by varying the amount of heat provided by a heat generating element by means of the electric power or the

  duration of a pulse applied to it.

  In this form of implementation of the image forming method according to the present invention, the transfer recording medium 1 is superimposed on a thermal head 20, and light is provided so as to completely cover the region 15. The wavelengths of the illumination light are therefore successively selected in a manner to react with the imaging elements 31 to be illuminated. For example, if the imaging elements 31 to be illuminated contain any of the vaporizable dyes capable of displaying the cyan, magenta and yellow colors, the irradiation is effected successively with light beams.

  having a wavelength A (C), A (M) and A (Y).

  More particularly, although the transfer recording medium 1 is illuminated with a light beam of wavelength A (Y) from the side of the vaporizable ink layer 1a, resistance heating elements 20b, 20d, 20e and 20f, for example, of the thermal head are caused to generate heat. Accordingly, of the image forming elements 31 containing a yellow vaporizable dye, the elements exposed to heat and light beam A (Y) 35 are cured as shown by hatching on the screen.

260 1 467

  Figure 1A (in Figure 1B and the following, the cured elements are also indicated by hatching).

  Then, as shown in FIG. 1B, while the vaporizable ink layer 1a is illuminated with a light beam of wavelength λ (M), resistance heating elements 20a, 20e and 20f are caused to generate light. heat, so that of the image forming elements 31 containing a magenta color vaporizable dye, those exposed to heat and light wavelength X (M) are cured. Further, as shown in FIG. 1C, while the wavelength luminous fluxes A (C) are produced, prescribed resistance heating elements are caused to generate heat, so that 'picture

  exposed to heat and light are cured, finally leaving a vaporizable portion (or a latent image) formed of uncured image forming elements 31. The vaporizable dye in the vaporizable portion is then transferred to a transfer carrier 8 in a subsequent vaporization step.

  In the vaporization step, the transfer recording medium on which the tent image is formed is disposed near or in contact with the transfer receiving medium, and heat is applied from the side of the carrier. recording by transfer or on the side of the transfer receiving medium, which has the effect that the dye. vaporizable 30 contained in the uncured image forming members 31 is vaporized and transferred to the transfer receptor medium to form a visible image on that medium. Accordingly, the heating temperature in the vaporization step must be determined so that the vaporizable dye contained in the elements

  31 of uncured image formation is selectively vaporized.

  If appropriate, in the vaporization step, it is advantageous for the vaporizable ink layer 5 not to come into direct contact with the transfer receiving medium, to prevent a veiled bottom from being

formed on this one.

  In the above embodiment, illustrated with reference to FIGS. 1A-1C, the entire surface of the thermal head 20 is illuminated with

  light, while the resistance heating elements of the thermal head 20 are selectively excited.

  On the other hand, while a given area of the transfer recording medium is uniformly heated, for example by energizing all the resistance heating elements of the thermal head 20 shown in FIG. 1A, illumination by light can be performed selectively or from an image, to form a similar multicolored image. More particularly, - light energy having a length

  A waveform modulated according to a recording signal and selected according to the vaporizable dye contained in an imaging element which is to be polymerized or depolymerized, is supplied together with thermal energy.

  In FIG. 1A, the thermal head 20 is excited completely and uniformly instead of selective excitation of resistance heating elements 20b, 20d, 20e and 20f, while the vaporizable ink layer 30 on portions corresponding to Resistance heating elements 20b, 20d, 20e and 20f are illuminated by a light beam of wavelength A (Y). Likewise, when a light beam of wavelength λ (M) is used, the entire thermal head 20 is excited and the portions corresponding to the resistance heating elements 20a, 20e and 20f are illuminated. Illumination by a light beam of

  wavelengths X (C) is conducted in the same way.

  In the explanation above, the means 5 for heating fully and uniformly

  the vaporizable ink layer has been considered to be a thermal head, for convenience of explanation, but it may be another uniform heating system such as a heating roller or a heating plate.

  The following is a description of materials used in the transfer recording medium wherein the degree of vaporization of the vaporizable dye can be influenced by polymerization or depolymerization of the functional component.

  As the vaporizable dye, for example, known sublimable dyes selected from disperse dyes comprising anthraquinone compounds and azo compounds can be used as representative examples, basic dyes comprising indolenin compounds and leucoaliphenyl compounds. phenoxazine as representative examples, etc. Of these dyes, however, those which have a vaporization initiation temperature (i.e.

  at which the vaporization starts) of 200 C or less.

  More particular examples of such dyes may include the following: Kayaset Yellow, Kayaset B Red and Kayaset Blue 906 (Trade Names, Nippon Kayaku K.K. yellow Resiren TGL, blue GN saddles, red Resiren TB and yellow Resorin GRN (trade names, products of the firm Bayer A.G.); yellow Dianix 6G-SE, bright yellow Dianix 5G-E, scarlet Dianix 3R-FE and scarlet Dianix PTB35 67 (trade names, products of the firm Mitsubishi Kasei Kogyo K.K.); yellow Miketon 5G, red Miketon BSF and blue Miketon FTK (trade names, products of the firm Mitsui Toatsu Kagaku K.K.); and yellow Sumicaron E4GL, red Sumicaron FBGL and blue Sumicaron 5 E-GRL (trade names, products of the firm Sumitomo

Kagaku Kogyo K.K.).

  The image forming elements forming the vaporizable ink layer contain a functional component and a vaporizable dye. The functional component can be advantageously a

  a substance that can undertake a reaction leading to a change in physical property or that can suddenly change the speed of such a reaction when supplied to it, or when irradiated with it, with different energies such as light and heat .

  A representative example of such a functional component may be a polymerizable component or a crosslinkable component such as a monomer, an oligomer or a polymer.

  Representative examples of the oligomer or polymer include compounds having an end- or side-chain reactive group, such as polyvinyl cinnamate, copolymer of p-methoxycinnamic acid-succinic acid half-esters, polyvinylstyrylpyridinium, polymethylvinylketone, polyethyleneglycolacrylate, polyethylene glycoldimethacrylate and polypropyleneglycoldiacrylate; or epoxy resins, resins of the unsaturated polyester type, polyurethane type resins, polyvinyl alcohol type resins, polyamide type resins, acid type resins

  polyacrylic, resins of the polymaleic acid type and silicone resins. Other representative examples include acrylic acid esters, acrylic acid amides, methacrylic acid esters and methacrylic acid amides.

260 1 467

  Examples of polymerizable monomers include ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, N, N'-methylenene-acrylamide, acrylate, and the like. Methyl methacrylate, cyclohexyl acrylate, benzyl acrylate, acrylamide, mesacrylamide, N-methylolacrylamide, N-diacetone-acrylamide, styrene, acrylonitrile, vinyl, butylene glycol di-methacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate,

  and triethylene glycol diacrylate.

  To trigger or activate the reaction of the polymerizable component, a reaction initiator such as a functional or sensitive component may optionally be added. The reaction initiator may advantageously be a radical generator such as azo compounds, organic sulfur compounds, carbonyl compounds and halogenated compounds. Representative examples illustrating the reaction initiator used for this purpose include: carbonyl compounds such as benzophenone, benzil, benzoyl ethyl ether and 4-N, N-dimethylamino-4'-methoxybenzophenone; organic sulfur compounds such as dibutyl sulphide,

  benzyl disulfide and decyl and phenyl sulphide; peroxides such as di-tert-butyl peroxide and benzoyl peroxide; halogenated compounds such as carbon tetrachloride, silver bromide and 2-naphthalenesulfonyl chloride; nitrogen compounds such as azobisisobutyronitrile and benzodiazonium chloride.

  In addition, to produce a vaporizable ink layer particularly suitable for use in forming a latent image under the joint action

260,146?

  of the light energy and thermal energy, the reaction initiator and the polymerizable component can be selected from the respective groups so as to produce an association having a large dependence on the rate of reaction to temperature, in that which concerns the reaction between a reaction initiator whose activity is manifested by

  light energy, and a polymerizable component.

  A preferred example of such an association can be obtained using a polymerizable monomer

  of the hot melt urethane acrylate type as the polymerizable component, and 2-chlorothioxanthone or ethyl p-dimethylaminobenzoate as a reaction initiator. In order to enhance the sensitivity, an acrylic resin can also be used as the binder.

  In addition, the vaporizable ink layer may also contain a stabilizing agent such as hydroquinone, p-methoxyphenol, p-tert-butylcatechol and 2,2'-methylene-bis- (4-ethyl-6-tetra) butylphenol). In order to promote the activation of the reaction initiator, the vaporizable ink layer may further contain, as a functional component, a sensitizer such as p-nitroaniline, 1,2-benzanthraquinone, p-p Dimethylaminobenzophenol, anthraquinone, 2,6-dinitroaniline and ketone

from Michler.

  On the other hand, a depolymerizing component, which is another example of the functional component, may be an oligomer or a polymer such as a poly styrene which contains ketone or quinone compounds, etc., as a promoter to promote depolymerization or decomposition.

  Examples of such ketone compounds may include copolymers such as vinyl methyl ketone and a monomer such as styrene, methyl methacrylate, butyl methacrylate, methyl acrylate, maleic anhydride and the like. Other examples of such quinone compounds may include copolymers such as 6-vinyl naphthoquinone and a monomer such as styrene, methyl methacrylate, methyl acrylate, and the like. In the case where the depolymerizable component is used as a functional component, it depolymerizes or decomposes when the vaporizable layer of vapor is exposed to different types of energy, so that vaporization of the vaporizable dye contained in the exposed portion to different kinds of energy can be favored. Accordingly, in the case where the depolymerizable component is used as a functional component, the portion exposed to different

  types of energy form a vaporizable portion.

  The vaporizable ink layer of the transfer recording medium may further contain a binder such as a resin, a wax or a mesomorphic compound.

  The binder may consist of resins such as homopolymers or copolymers of polyester type, polyamide type, polyurethane type, polyurea type, polyvinyl type, silicone type, polyacetylene type and polyether type; waxes comprising vegetable waxes such as candelilla wax, carnauba wax and rice wax, animal waxes such as beeswax and spermaceti, mineral waxes such as ceresin wax and mountain wax , an oil wax such

  than paraffin wax; and synthetic waxes comprising polyethylenic wax, sasol wax, montan wax derivatives, paraffinic wax derivatives, hardened castor oil, hardened castor oil derivatives, fatty acids such as acid. stearic

  as fatty acid amides, fatty acid esters. These resins or waxes can be used individually or in the form of a mixture of two

or more than two of them.

  In addition, the mesomorphic compound used as a binder may comprise: cholesterol hexanoate, cholesterol decanoate, cholesterol maminocarbonate, cholesterol methyl carbonate, 4'-methoxybenzylidene-4-acetoxyaniline, 4'-methoxybenzylidene- 4-ethylaniline, 4'-ethoxybenzylidene-4-cyananiline, N, N'-bisbenzylidene-3,3'-dimethoxybenzidine, etc. The vaporizable ink layer may advantageously comprise, on the basis of its total weight, for example 0.1 to 10% of a vaporizable dye, 20 to 95% (especially 50 to 90%) of a functional component and 0.001 to 20% (especially 1 to 10%) of a reaction initiator. In addition, the content of a binder can go

  preferably from 0 to 80%, preferably from 0 to 50%.

  The vaporizable ink layer may be formed, for example, by solvent coating, and its thickness may preferably be from 1 to 20 μm,

in particular from 3 to 10 Vm.

  The following is a description of materials used in one embodiment of the support

  transfer recording in which a vaporizable dye reacts on its own. In such an embodiment, each imaging member 31 may comprise a vaporizable dye carrying a reactive group, a reaction initiator, a binder and an additional component. An image forming method using such a transfer recording medium may be similar to that described

  above with reference to Figures 1A to 1C.

26 0 1 4 6 7

  In the present invention, the degree of

  The reaction of the vaporizable dye is remarkably favored in the case where several kinds of energy such as light and heat are provided, compared with the case where only one type of energy is provided.

  Such a characteristic can be achieved, for example, by promoting the dependence of photoreaction on temperature. More particularly, for example, it is effective to control the glass transition temperature or melting point of the binder to maintain the vaporizable ink layer in the solid state up to an intermediate temperature between the values.

  in the heated state and in the unheated state.

  In this embodiment, for example, a sublimable dye carrying a reactive group

  such as an allyl, methallyl, acryl, methacryl and styryl group may be used as a vaporizable dye.

  Representative examples of these sublimable dyes include the following dyes:

  1,5-bis (allylamino) -4,8-naphthoquinone, 1-allylamino-5-methylamino-4,8-naphthoquinone, 1-allylamino-5-ethylamino-4,8-naphthoquinone, 4- (2,2-dicyanovinyl) -N, Ndiallylaniline, 4- (2,2-dicyanovinyl) -N-methacryl-N-methylaniline, 4- (2,2-dicyanovinyl) -N-methallyl-N25-methylaniline, 3-methyl-4- (2,2-dicyanovinyl) -N, N-diallylaniline , 4-Tricyanovinyl-N, Ndiallylaniline, 4-tricyanovinyl-N-methyl-N-acrylaniline and 3-vinyl-4-tri-ylovinyl N, N-dimethylaniline.

  Representative examples of the reaction initiator used for this purpose include: carbonyl compounds such as benzophenone, Michler's ketone, benzoin ethyl ether, 2chlorothioxanethone and 4-N, N-dimethylamino-4 methoxybenzophenone, organic sulfur compounds such as dibutyl sulfide and benzene disulfide;

  Zyle; peroxides such as di-tert-butyl peroxide and benzoyl peroxide; halogenated compounds such as carbon tetrachloride, etc. In the case where the vaporizable dye, when exposed to several kinds of energy such as light and heat, is chemically bonded to another component in order to thereby lower the degree of vaporization, it can be used in particular a linker component carrying a reactive group (hereinafter referred to as "reactive binder"). In this case, when exposed to several kinds of energy, the vaporizable dye and the reactive binder can be chemically bonded

  to lower the degree of vaporization.

  A polymerizable prepolymer, a polymerizable oligomer, a crosslinking agent and the like can be used as the reactive binder. Representative examples of this binder include: polymerizable prepolymers such as epoxy resins, unsaturated polyester type resins, polyurethane type resins and polyacrylic acid type resins; polymerizable oligomers such as diethylene glycol diacrylate, triethylene glycol diacrylate and polyethylene glycol dimethacrylate; crosslinking agents such as ethylene glycol diacrylate, propylene glycol diacrylate and 1,4-butanediol diacrylate; etc. On the other hand, raw materials analogous to the reagent binders mentioned above and without a reactive group can be used as binders not carrying a reactive group. It is also possible to use ethylcellulose, hydroxyethylcellulose, cellulose acetate propionate, alkyd resins, polyamide resins, water-soluble acrylic resins, a vinyl alcohol polymer, and the like. In addition, in the case where the vaporizable ink layer must be solid at ordinary temperature, it is possible to add to the reactive binder the binder indicated above not carrying a reactive group, as a compensating agent. The vaporizable ink layer may also further contain a stabilizing agent such as hydroquinone, p-methoxyphenol, p-tert-butylcatechol and 2,2'-methylene-bis- (4-ethyl-6-tert) butylphenol). In order to promote the activation of the reaction initiator, a sensitizer such as p-nitroaniline, 1,2-benzanthraquinone, p, p 'may also be added to the vaporizable ink layer. dimethylaminobenzophenol, anthraquinone, 2,615 dinitroaniline and Michler's ketone. In the case where the vaporizable dye is itself reactive, the vaporizable ink layer may advantageously contain, on the basis of its total weight, for example 0.1 to 10% of the vaporizable dye 20 and 0.001 to 20% (especially 1 to 10%) of the reaction initiator. Moreover, the one in a binder can go

  preferably from 0 to 80%, preferably from 0 to 50%.

  In the case where the vaporizable ink layer contains the reactive binder, its content may preferably be from 20 to 95%. In this case, the thickness of the vaporizable ink layer may also preferably range from 1 to 20 Vm,

in particular from 3 to 10 Vm.

  In order to make the transfer recording medium in a form suitable for use in forming a multicolor image, the image forming elements containing different vaporizable dyes can advantageously be sensitive to different wavelengths. . As described above, when the vaporizable ink layer 35 is composed of a number (n) of image forming element types with respect to the colors of the vaporizable dyes, the vaporizable ink layer should advantageously comprise a combination of n types of imaging elements for respective types of vaporizable dyes and each permitting a sudden change in reaction rate under the effect of irradiation with a fluorescent light.

particular wavelength.

  In order to obtain such an association of imaging elements, it is possible to use, for example, a combination of sensitizers. Examples of such an association include, in the case of a two-color recording system, an association formed of a sensitive sensitizer at about 400-500 nm such that:>,> CH = CH- \ N , or "CH3

N 3

N g CH = CH 'N c 3

N /% / CH3

  and a sensitive sensitizer at about 480-600 nm, such as:

S S

3, _CH-CH = S

I o I

C2H5 C2H5

H3C -a N 4 "'- 2 NO N

KOOC-CH2

  In this case, the sensitivity regions of the two above types of sensitizers overlap each other in the range of 480 to 500 nm, but this is a low sensitivity region for both types of sensitizers. So, they

  can be almost completely separated from each other, if necessary, by the use of appropriate light sources.

  A sensitivity separation adapted to the three-color image forming element system can be achieved by the use of a azole compound having a sensitivity in the range of 340 to 400 nm or a halogenated compound having a sensitivity. in the range of 300 to 400 nm in combination with the above sensitizers, so that a pure color recording system can be developed. In addition, one of the combinations of 2-chlorothioxanthone / ethyl p-dimethylaminobenzoate and dichlorobenzophenone / ethyl p-dimethylaminobenzoate can also be used as a combination of reaction initiators. Light sources of a fluorescent light having a maximum wavelength of 390 nm and fluorescent light having a maximum wavelength of 313 nm may be used in conjunction with the reaction initiator combination set forth above. above. To achieve the same degree of reaction (i.e., the same level of transfer density), the desired level of illumination energy is assumed to be 1 (reference) for an association - 0, it has 4 (times) this value for the association (-si 1.1 times for the association - G and 5 times for the association -0) results that if the light source 0 is used at the level of energy of illumination equal to 1 and if the

  Light source O is used at illumination energy level equal to 1.1, the reaction initiator systems and can be excited separately.

  In the embodiment shown in FIGS. 1A to 1C, the vaporizable ink layer 1a is made as a coating layer made of image forming particles, but it can also be a layer continuously uniform coating coating 10. In addition, the image-forming particle elements may also be in the form of capsules each comprising a core and an envelope surrounding this core. In the case of image forming capsular elements, the vaporizable dye and the functional component are generally enclosed in the core. In order to obtain a multicolored image, it is advantageous to use image forming elements in particles or in capsular particles. Such image forming elements 20 may advantageously be distributed at 50% of the maximum packing state, relative to the projection area on the substrate. In the case where the vaporizable ink layer is formed of image forming capsular elements, the envelopes of the imaging elements are broken in the vaporization step to vaporize the vaporizable dye contained in the material constituting the material. in order to form an image on a transfer receiver medium. Accordingly, the heating temperature in the vaporization step is determined so that the vaporizable dye

  in the vaporizable portion is selectively vaporized and transferred.

  On the other hand, the microcapsule shell may be formed of, for example, a material comprising gelatin, gum arabic, cellulose resins, and the like.

  such as ethylcellulose and nitrocellulose, polymers such as urea-formaldehyde resin, polyamides, polyesters, polyurethane, polycarbonate, maleic anhydride copolymers, vinylidene chloride polymer, polymer, and the like. vinyl chloride, polyethylene, polystyrene

  and a polymer of ethylene terephthalate.

  The microcapsules are produced according to an average particle diameter, preferably measuring from 10 to 20 μm, in particular from 3 to 10 microns, with a shell thickness in the preferred range of 0.1 to 2 microns, in particular 0.1 at 0.5 micrometer. The microcapsules may advantageously be attached to a substrate, for example, using a binder such as a vinyl alcohol polymer and an epoxy adhesive. In this case, the binder intended for coating the microcapsules is used, for example, in an amount chosen so as to form a thickness of 0.1 to 20 microns, for example. The thickness of the binder may advantageously be not less than 0.1 micrometer and not be less than the average diameter of the microcapsules, in particular not less than 0.1 micrometer and not more than half the average particle diameter indicated below. above, in particular not less than 0,1 micrometres and not more than

  of the average particle diameter indicated above.

  In addition, it is advantageous not to completely cover the microcapsules of the binder.

  In the trans-recording medium used in the present invention, it is possible that the radical reactivity of the vaporizable ink layer is suppressed due to oxygen in the air. To overcome this disadvantage, it is advantageous to create a protective layer against oxygen by the application of an aqueous solution of polyalcohol.

  vinyl containing a small amount of a surfactant on the vaporizable ink layer. The protective layer against oxygen can be removed by washing with water after the formation of the latent image. When the imaging elements are in the form of microcapsules, it is possible that the envelopes function as an oxygen barrier layer. The substrate to be used in the transfer recording medium according to

  The present invention is not particularly limited, but it may be a known material such as polyester, polycarbonate, triacetylcellulose, "nylon" and polyimide, for example in the form of a film or sheet.

  In the case where, in the present invention, the vaporizable ink layer is composed of the image forming elements, for example, the components described above may be melt blended or spray dried to form small image forming elements, and then applied to a substrate, for example using a dispersion of these components, so as to form a vaporizable ink layer. In the case where a micro-capsular imaging element is used, the microcapsule can be formed by known methods such as the process.

of coacervation.

  The transfer recording medium used in the present invention may be produced, for example, as follows.

  The various components forming the vaporizable ink layer such as the functional component, the reaction initiator, the sensitizer, the stabilizing agent, the vaporizable dye, etc., can be melt blended and applied to one another. substrate by means of an applicator, etc., to form a transfer recording medium according to the present invention. In the case where the vaporizable ink layer 5 consists of imaging elements, for example, the above components can be mixed and processed into small image forming elements by spray drying, etc. for the respective colors, and the resulting respective color image-forming elements are sufficiently mixed with a binder such as a polyester-type resin in a solvent such as methyl ethyl ketone or ethylene glycol diacetate and the mixture is applied by a solvent coating process on a substrate such as a polyimide film, the application being followed by drying, for example at 80 ° C for 3 minutes to drive off the solvent to form a layer vaporizable ink. We can get this way

  a desired transfer recording medium.

  In case the imaging elements

  are in the form of microcapsules, they are produced by a process such as coacervation and can be applied to a substrate by a solvent-coating method similar to that described above with respect to the image-forming elements of the invention. particles.

  In the image-forming method according to the present invention, there can be provided on the surface of a transfer-receiving medium, in order to promote the adhesiveness or the color development of the dye, a developer layer comprising resins such as saturated polyester type resin, ethylene vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyamide type resin, chloride type resin

  of vinylidene and a urethane resin.

  Further, in the transfer recording medium according to the present invention, fine particles which are not melted or softened and which do not adhere to the transfer receiving medium at a temperature at which the vaporizable dye is vaporized are advantageously provided on the surface of the vaporizable ink layer in a distri-molded form, or such particles are incorporated in the vaporizable ink layer. This is done because the binder constituting the vaporizable ink layer is not transferred to a transfer receiving medium. In the case where such fine particles are incorporated into the vaporizable ink layer, they may be preferably

  protrude on the surface of the vaporizable ink layer.

  Examples of such fine particles may be advantageously ceramic particles such as titanium oxide, silicon oxide and silicon carbide particles; glass beads; and cross-linked polystyrene beads, polysulfone, etc. These fine particles may advantageously have an average diameter of about 2 to 200 microns. The average particle diameter may range from 2 to 80 micrometers in the case where the fine particles are distributed on the surface of the vaporizable ink layer, and can range from 20 to

  micrometers in case they are incorporated in the vaporizable ink layer.

  In place of the fine particles above, it is possible to provide a mesh material on the surface of the vaporizable ink layer to prevent its transfer. Such mesh material may be, for example, a nonwoven fabric formed of

glass fibers.

  In the image forming method according to the present invention, the vaporizable ink layer is exposed to energies of different types.

  The following is a summary of several modes of application of energy, in addition to the indications that have been

data above.

  (1) A reaction initiator and a functional component are arranged in the vaporizable ink layer in an arrangement such that they are mixed with each other at the point where pressure is exerted (eg The reaction initiator is contained in capsules which are broken under pressure by causing mixing between the reaction initiator and the functional component), and the reaction initiator is excited only by heating. . The vaporizable ink layer is exposed to a pressure energy and a thermal energy, at least one of the energies corresponding to a recording information signal, so as to form a latent image portion having a degree of varied vaporization of the dye

  vaporizable present in the vaporizable ink layer.

  (2) A reaction initiator which can be excited only by exposure to light and a functional component are disposed in the vaporizable ink layer so as to be mixed with each other at an exposed portion. at a pressure. A pressure energy and a light energy are applied to the vaporizable ink layer, at least one of these energies corresponding to an information signal

  for forming a latent image portion having a varying degree of vaporization of the vaporizable dye in the vaporizable ink layer.

  (3) A reaction initiator which can be excited by exposure to heat energy and light energy, and a functional component are arranged in the vaporizable ink layer so as to be mixed with each other at the same temperature. a portion exposed to pressure. Pressure energy, thermal energy, and light energy are applied to the vaporizable ink layer, at least one of these energies corresponding to a recording information signal, so as to form a portion

  latent image having a varying degree of vaporization of the vaporizable dye in the vaporizable ink layer.

  The transfer recording medium 15 according to the present invention may be used, for example, in an apparatus as shown in FIG.

Figure 2.

  In FIG. 2, the transfer recording medium 1 of the present invention is wound in the form of a feed roll 2 which is removably disposed in the main body M of an apparatus. More particularly, the feed roller 2 is removably mounted on an axis 2a disposed in the main body M and freely rotatable. The transfer recording medium 1 is unwound in the direction of the arrow a and then rolls on

a coil 6 of winding.

  The unwanted transfer recording medium 1 of the feed roll 2 first reaches a recording section (or latent image forming section) 3. The recording section 3 comprises a heating device and an illumination device. The heater comprises a recording head 3a whose surface is provided with a row 3b of in-line heating elements capable of generating heat corresponding to an image signal. The heater array 3b is disposed so that it can contact the substrate side of the transfer recording medium 1 under a predetermined pressure caused by the reaction voltage in the movement of the recording medium by transfer. The image signal mentioned above is produced incidentally, for example, O10 by a reproduction device, an image analyzer

  or the command of an "electronic board" (that is, an apparatus in which pictures written on a board can be printed directly), etc. (not shown) according to the uses that are made of it.

  Furthermore, on the side of the vaporizable ink layer opposite to the recording head 3a, three fluorescent lamps 3c, 3d and 3e are arranged as illumination means. The fluorescent lamps 3c, 3d and 3e illuminate, respectively, the transfer recording medium with luminous flux of different wavelengths AY, AM and AC.

  The description of the transfer section 4 is now given.

  The transfer section 4 is disposed downstream of the recording section 3 above, with respect to the direction of movement of the transfer recording medium 1, and comprises, as shown in FIG. 2, a transfer roller 4a rotated in the direction of the arrow b, and a pressure roller 4b which is in contact with the transfer roller 4a under pressure. The transfer roller 4a comprises, for example, an aluminum roller whose surface is covered with silicone rubber, and is made in such a way that

260 1467

  its surface can retain the heat provided by

  a heating device 4c provided inside.

  In addition, the pressure roller 4b comprises, for example, an aluminum roll covered with silicone rubber and is arranged in such a way that

  a pressure force is caused to act in the direction of the transfer roller 4a under the effect of a member exerting a pressure such as a spring (not shown). This pressure roller 4b is particularly effective in the case where the imaging elements comprise microcapsules.

  In addition, paper 8 as a transfer receiving medium, loaded in a magazine 7, is driven and loaded into the transfer section 4 by means of a feed roller 9, and a pair

  of registration rolls 10a and lob, with a synchronism such that the paper can be superimposed on a region of the transfer recording medium 1 in which the latent recording image is formed.

  The transfer recording medium 1 of the present invention is now loaded successively by the feed roller 2 and its vaporizable ink layer is exposed to light and heat, at least one of which corresponds to an image signal, in the recording section 3, so that a latent recording image comprising a vaporizable portion and a non-vaporizable portion is formed as described above with reference to Figs. 1A to 1C . The vaporizable dye contained in the vaporizable portion formed in the recording section 3 is transferred to the transfer receptor support 8 in the transfer section 4 so as to form an image transferred thereto. The transfer receiver support 8 on which the transferred image 35 is formed is discharged into a plate 11 provided for

this effect.

  In the image forming method according to the present invention, the energy input for the formation of the latent recording image in a vaporizable ink layer and the energy input for the vaporization of A vaporizable dye is functionally separated, so that the energy supply conditions are moderate, since the transfer or vaporization energy does not need to be precisely adjusted. For example, the vaporization energy can be provided by uniform energy without signaling. As a result, in the present invention, a printing speed can be increased and a large recording can be made.

  speed can be achieved easily.

  A thermal head used in the conventional thermal transfer recording apparatus has a thermal response rate ranging from about 1 to 5 milliseconds, at maximum speed. When a thermal head is driven in a shorter repetition cycle, heating and cooling can not be sufficiently carried out in the cycle and this results in insufficient heating or remanent heat due to insufficient cooling, which leads to to a degradation of the quality of the image. This is one of the obstacles to achieving a high-speed operation. On the other hand, in the present invention, several kinds of energy such as light and heat are used, when a thermal head and illumination by light are combined, the influence of insufficient cooling and heat. The remanence of the thermal head is suppressed or moderated because the degree of vaporization of the vaporizable dye can be changed only when the illumination is combined with the heat released by the thermal head. As a result, even a conventional thermal head can be used for a recording operation in a shorter cycle, so that high speed recording can be easily achieved by the present invention. Since a latent image is formed in the vaporizable ink layer by the fact that several kinds of energy are provided in the present invention, the variation of the vaporization degree can be easily adjusted in stages, compared to a process conventional thermal transfer recording system in which thermal energy is used alone for the formation of a latent image. In addition, a source of energy such as light having a high speed of response and being adapted to a gradual intensity adjustment can be used as one of the various energy sources, and it is therefore possible to form an image of medium hue. For example, if three stages of intensity or illumination time are combined with heating, four stages

  gradation (three steps plus a step without heating) become possible.

  Although it is also desirable that such adjustment be done at high speed, the joint use of energy such as light having a high speed of response makes possible a

  recording in medium hue at high speed.

  In addition, in the present invention, by varying the supply conditions of different kinds of energy successively in short periods,

  a multi-color transferred image can be obtained at a high speed without requiring complex movement of the transfer recording medium or the transfer receiving medium, as required by the conventional method of trans-record recording.

  thermal fertility. Accordingly, an apparatus for carrying out the image forming method according to the present invention is of simple structure, and is easy to make in a compact, lightweight and inexpensive form.

  The present invention is described below by examples.

Example 1

  The components shown in Table I were mixed and the resulting mixture applied to a 6 μm thick aramid film by solvent coating, protected from light, to form a layer of vaporizable ink of 4 Vm thick over which was applied a layer of PVA (polyvinyl alcohol) 2 μm thick as an oxygen protective layer, in order to make a transfer recording medium compliant

to the present invention.

TABLE I

25 30

* Component Composition Parts (Merable poly-β1H3 component) aC- -c ± O Meridable poly-IU 40 prepolymer CH3 αCXo O'CH2-CCH = C2 OH (Mp = 5x103 2-chlorothioxanthone initiator 4 reaction Ethyl pdimethylaminobenzoate 12 Polyvinylbutyral Binder, Mp = 5000 34 (product of General Science Co.) Sublimable Blue Yayaset 156 (produced by Nippon Kayaku KK) * 1,100 g of methyl methacrylate and 100 g of methacrylate diglycidylmethyl are copolymerized in 1 liter of benzene in the presence of N, N'-azoisobutyronitrile (initiator) at 60 ° C. for 30 minutes The resulting copolymer is redissolved in 1 liter of benzene, to which 50 g of acrylic acid have been added and 5 g of hydroquinone, and the mixture is stirred at 60 ° C. for 2 hours in order to prepare a polymerizable prepolymer indicated in Table I. The molecular structure of the prepolymer appears to be such that

  shown in Table I, based on infrared analysis.

  The transfer recording medium thus prepared in accordance with the present invention is cut into 210 mm wide sheets, the sheets are loaded into an apparatus as shown in Fig. 2 and a transfer image is formed on paper without cellulose, as a receiving medium

transfer.

  In this example, a thermal head of 8 points per mm is used, and a fluorescent lamp of 40 W with a maximum wavelength of 370 nm is used as the light source. In addition, a heating roll 25 is used in a vaporization stage, the surface temperature of which is set to 100.degree.-120.degree.

  Furthermore, the transfer recording medium on which a latent recording image was formed, prior to its exposure to the vaporization step, was removed once from the apparatus and washed with water to remove the PVA, then the transfer recording medium has been put back into place in the apparatus shown in FIG.

to form a transfer image.

  Image formation was performed using such an apparatus and following the sequence shown in Fig. 3, so as to obtain a blue image. The time diagram shown in FIG. 3 shows the light pulses of a fluorescent lamp (upper part) and the control pulses of a thermal head (lower part). A similar image formation is further effected by changing the duration of the control pulse of the thermal head from 0 to 17 milliseconds, which varies the density of the recorded image as a function of the duration of the control pulse (17-T), as shown in the graph of FIG. 4. The image density is also shown in FIG.

  4 and expressed in units of OD (optical density).

Example 2

  The components shown in Table II were mixed to prepare a core material, which was then microencapsulated

as follows.

TABLE II

  F Component Composition Parts (Poly (Me erable component) miserable) H2C = CHOOC.CH2CH2- '/ CH2CH2COOCH = CH 75

2 22 '2 2 2

Polymerizable monomer J O

0 'IN 0

CH2CH2COOCH = CH2

  (Trade name: Aronix M-315, product of Toa Gosei Kagaku firm Kogyo KK) 2-chlorothioxanthone initiator 5 ethyl pdimethylaminobenzoate reaction 10 Sublimation dye Blue Kayaset 136 (produced by mable firm Nippon Kayaku KK) 10 o o C, C> g of a mixture of components shown in Table II are mixed with 20 g of methylene chloride. The resulting mixture is then mixed with a solution obtained by dissolving a cationic or nonionic surfactant having a hydrophilic balance.

  lipophilic at least equal to 10 and 2 g of gelatin in 200 ml of water, and the mixture is then emulsified using a homogenizer at 800-10,000 rpm, heating to 60 C to obtain droplets 10 oil having an average diameter of 26 micrometers.

  The mixture is then stirred for 30 minutes at 60 ° C. and then the methylene chloride is distilled off to give droplets of oil having

  average diameter of about 10 micrometers.

  A solution obtained by dissolving 1 g of gum arabic in 20 ml of water is then added to the mixture prepared above. A 5% solution of NH 4 OH (aqueous ammonia solution) is added to the resulting mixture while cooling slowly to adjust the pH to a value equal to or greater than

  11, and thus a suspension of microcapsules is prepared.

  1.0 ml of 20% aqueous glutaraldehyde solution is then slowly added to the suspension.

  to harden the envelopes of the microcapsules.

  The suspension is subjected to a solid-liquid separation operation by means of a suction filter, and the solid material is dried at 35 ° C. for 10 hours in a vacuum drying device to obtain microcapsular formation elements. image having an average diameter of particles of

micrometers.

  A binder (polyesterTP220, a product of Nippon Gosei Kagaku Kogyo K.K.) was separately applied to a 6 μm thick polyethylene terephthalate (PET) film to form a binder layer having a thickness of 2-3 μm. The microcapsules prepared above are applied to the binder layer away from the light to form a layer of vaporizable ink on the film, so as to prepare a compliant transfer recording medium.

to the present invention.

  The thus prepared transfer recording medium is cut into a 210 mm wide sheet which is loaded into the same apparatus as in Example 1, and a transfer image is formed on a transfer receiving medium. However, in this example, the surface temperature of the roll

  heating is set at 120-130 C.

  The formation of the image is carried out using such apparatus and following a sequence

  illustrated in FIG. 5, so that clear images are obtained on the transfer receiver medium.

Example 3

  The components shown in Table III are mixed separately to prepare three kinds of core materials of imaging elements Y, M and C, which are, respectively, microencapsulated in the same manner as in the present invention. Example 2 to prepare three types of respective image forming elements Y, M and C having particle diameters mainly in the range of 8 to

12 pim.

TABLE III

  Component Element Y Element M Element C Parts (Polymerizable Component) 60 Merable Poly- (CH2 = CHCOOCH2-CH2-O-CO-NHH) Monomer 60 Initiator Irgacure 907 Michler 2-methyl-6-ethoxyeaction ketone (product of the + benzophenone carbonylthioxan- Ciba-Geigy firm (8: 2 mixture) thone Corp.) PMMA binder (Elvasite 2041, product of the Du Pont firm) 20 Sublimation dye-Yellow.Kayaset Red Kayaset B Blue Kayaset 906 mable AG (product of the (product of the firm Nippon firm Nippon company Nippon Kayaku KK Kayaku KK) Kayaku KK) W Nl OM% C, 0% -'a separately formed as in Example 2, a layer of binder on a PET film with a thickness of 3.5 μm, treated to withstand heat, the three types of image forming elements Y, M and C prepared above are applied, each

  in an equal amount, on the binder layer while operating in the absence of light to form a vaporizable ink layer so as to prepare a transfer recording medium in accordance with the present invention.

  The transfer recording medium thus produced is cut into a 210 mm wide sheet which is placed in the same apparatus as that shown in FIG. 2, and a transferred image is formed on a transfer receiving medium. in a sequence shown in Figure 6, and thus clear images are obtained. In this example, cellulose-free paper with a polyester-type resin layer is used as the transfer-receiving support. In addition, a thermal head of 8 points per mm is used and the light sources consist of three 40 W fluorescent lamps having, respectively, maximum wavelengths of 313 nm, 360 nm and 420 nm. A heating cylinder whose surface temperature is set to 120-130 ° C is

  used in a vaporization step.

Example 4

  The components shown in Table IV are mixed and the resulting mixture is applied to a 6 μm thick PET film by solvent coating away from light to form a vaporizable ink layer of 4 μm. Vm thick. Next, a 200 g / m 2 mesh fabric comprising a non-woven fiberglass fabric 6 Vm thick is disposed on the vaporizable ink layer, and then PVA is applied to the mesh fabric to form a layer. the oxygen shielding device is 2 μm thick, so as to provide a transfer recording medium according to the present invention. oo-4 oo oo oo ooo ooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo ZHD = HD-O-gHOHZHOOOOD HHOOO o -e-ZH) (o-ZHosaqiua uoTiIsoduoD ouesodmoD AI lVaIVaav

260 1 467

  The transfer recording medium thus made in accordance with the present invention was cut into a 210 mm wide sheet which was placed in an apparatus as shown in FIG. 2, and a transferred image was formed on a carrier

  non-cellulosic paper transfer receiver.

  In this example, a thermal head of 8 dots per mm was used and, as a light source, a 40 W fluorescent lamp having a maximum wavelength of 370 nm. In addition, a heating roller whose surface temperature was set at 100-120 ° C. was used in a vaporization step. Moreover, the PVA was removed by washing with water before the step

  of vaporization, as in Example 1.

  The formation of the image was performed using the same apparatus and following the same sequence as in FIG. 5, and thus clear images of average tone were obtained. Imaging was further effected using non-cellulosic resin-coated paper, so that the image density was increased and images

clearer were obtained.

Example 5

  The components shown in Table V were mixed separately to prepare three kinds of Y, M and C image forming cores which were, respectively, microencapsulated by the urea-formalin method of to obtain three kinds of elements Y, M and C of image formation. The resulting microcapsules were classified, respectively, by means of a classifier so that they have respective particle diameters.

from 8 to 13 micrometers.

TABLE V

  Component Element Y Element Element C Parts Reactive Binder 30

(CH2 = CHCOOCH2-CH2-O-CO-NH-G-CH2

  Initiator of Irgacure 907 Michler's ketone 2-methyl-6-ethoxyreaction (product of + benzophenone carbonylthioxanthone 8 firm CibaGeigy Corp.) PMMA binder (Elvasite 2041, product of the firm Du Pont) 60

  _. ......, ......... DTD: Sublimethyl 4- (2,2-dicyano-4-tricyanovinyl) allylamino-5mable dye) -N-allyl-N-allyl-N- methylmethylamino-4,8N-methylaniline aniline naphthoquinone O0 -5-

  A binder layer is formed separately in the same way as in Example 2 on a 3.5 μm thick PET film treated to resist heat. The three types of imaging elements Y, M, and C, each in equal amounts, were applied to the binder layer away from light to form a vaporizable ink layer so as to prepare and a transfer recording medium according to the present invention.

  The transfer recording medium thus prepared is cut into a 210 mm wide sheet which is put into place in the same apparatus as in FIG. 2, and a transfer image is formed on a transfer receiving medium in accordance with the same Frequency as in FIG. 6, which makes it possible to obtain clear and staggered images. In this example, non-cellulosic paper coated with a polyester type resin is used as the transfer receiving medium. In addition, an 8-point thermal head at 20 mm is used with, as the light source, three 40 W fluorescent lamps having respective lengths of 313 nm (XY), 360 nm (AM) and 420 nm (AC). A heating roller whose surface temperature is set at 120-130 ° C is used in the vaporization step. Example 6 A mixture was prepared as in Example 1 except that 34 parts of PMMA were used as binder in Table 1. The resulting mixture is then applied to a 6 mm thick aramid film shielded from light to form a layer of vaporizable ink of 4 μm thickness, followed by glass beads having a diameter. A mean individual of 10 Vm is distributed over the vaporizable ink layer at a rate of about 5x105 cn beads. In addition, PVA is applied to the glass beads to form an oxygen barrier layer as in Example 1, so as to prepare a recording medium.

  by transfer according to the present invention.

  Using the above transfer recording medium, transfer images are formed on cellulosic paper as in Example 1, which allows clear images to be obtained on the transfer receiving medium. On the other hand, the PVA is removed by washing with water before a vaporization step, as in Example 1.

Claims (28)

  A method of forming an image, characterized in that it comprises: taking a transfer recording medium comprising a substrate (1b) and a vaporizable ink layer (1a) disposed on the substrate, said a vaporizable ink layer (1a) containing a vaporizable dye and being capable of modifying the degree of vaporization of the vaporizable dye by exposure to several kinds of energy; exposing the vaporizable ink layer (la) to the several kinds of energy under conditions such that at least one of the kinds of energy corresponds to a recording information signal, so as to form a vaporizable portion in the vaporizable ink layer (la); and vaporizing the vaporizable dye present in the vaporizable ink layer (1a) so as to transfer the vaporizable dye to a transfer receiving medium so as to form an image corresponding to the vaporizable portion on the transfer receiving medium.   2. Process according to claim 1, characterized in that the different kinds of energy are thermal energy and light energy.   3. Process according to claim 1, characterized in that the degree of vaporization of the vaporizable dye present in a portion of the vaporizable ink layer which is offered by the different energy sources is reduced.   Process according to claim 1, characterized in that the degree of vaporization of the vaporizable dye present in a portion of the vaporizable ink layer produced by the different kinds of energy is increased.   5. Process according to claim 1, characterized in that the vaporizable dye is a sublimable dye.   The method of claim 4, wherein the vaporizable ink layer is a distributed layer of imaging elements.   each containing said vaporizable dye.   7. A method according to claim 6, characterized in that the imaging element 10 comprises a capsule formed of a core containing the vaporizable dye and a casing encapsulating the core. 8. A method of forming an image, characterized in that it comprises: taking a transfer recording medium comprising a substrate and a vaporizable ink layer disposed on the substrate which comprises a distributed layer of elements of image formation capable of generating a plurality of colors, each imaging element containing a vaporizable dye capable of generating one of the different colors, each imaging element being capable of changing the degree of vaporization of the image. vaporizable dye by exposure to different kinds of energy in a particular energy condition depending on the color of the vaporizable dye contained therein; exposing the vaporizable ink layer to the different kinds of energy under respective energetic conditions which correspond, respectively, to the different colors in question, and in correspondence with a recording information signal, so as to form a portion vaporizable in the vaporizable ink layer; and vaporizing the vaporizable dye in the vaporizable ink layer so as to transfer the vaporizable dye to a transfer receiving medium, thereby forming an image corresponding to the   vaporizable portion of the transfer receptor support.   9. The method according to claim 8, characterized in that the imaging element   comprises a capsule formed of a core containing the vaporizable dye and an envelope encapsulating the core.   10. Process according to claim 8, characterized in that the different kinds of energy 10 are thermal energy and light energy.   11. The process of claim 10   characterized in that the wavelengths of the light energy correspond, respectively, to the different colors, and the thermal energy is modulated on the basis of said recording information.   A method according to claim 10, characterized in that the light energy whose wavelength is modified in a manner which corresponds to the different colors is modulated on the basis of the recording information, while energy   thermal is applied uniformly.   13. Process according to claim 8, characterized in that the degree of vaporization of the vaporizable dye present in a portion of the vaporizable ink layer which is offered by the different kinds of energy is lowered.   14. Process according to claim 8, characterized in that the degree of vaporization of the vaporizable dye present in a portion of the vaporizable ink layer which is offered by the different kinds of energy is increased.   15. Process according to claim 8, characterized in that the vaporizable dye is a dye that can be sublimated.   16. Transfer recording medium, characterized in that it comprises a substrate (1b) on which is disposed a layer (1a) of vaporizable ink, said layer containing a vaporizable dye and being capable of modifying the degree of vaporization vaporizable dye under the effect of different kinds of energy. 5 17. Support according to claim 16, characterized in that the vaporizable ink layer contains a functional component and the degree of vaporization can be modified on the basis of a reaction. of the functional component.   18. Support according to claim 16, characterized in that the vaporizable ink layer is a distributed layer of imaging elements.   each containing said vaporizable dye.   19. Support according to claim 16, characterized in that a protective layer against   the oxygen is disposed on the vaporizable ink layer.   20. A transfer recording medium, characterized in that it comprises a substrate and a vaporizable ink layer disposed on said substrate, which comprises a distributed layer of imaging elements capable of generating a plurality of images. colors, each imaging element containing a vaporizable dye capable of generating one of the different colors, each imaging element being capable of modifying the degree of vaporization of the vaporizable dye under the influence of different kinds of energy in a particular energy condition that depends on the color of the vaporizable dye contained therein. 30 21. Support according to claim 20, characterized in that the imaging element comprises a capsule consisting of a core containing the vaporizable dye and a casing encapsulating the core. i 22. Support according to claim 21, characterized in that the envelope behaves as   a protective layer against oxygen.   23. Support according to one of claims 5 16 and 20, characterized in that the different kinds   of energy are thermal energy and light energy.   24. Support according to claim 20, characterized in that the imaging element 10 contains a functional component, and the degree of vaporization is modifiable on the basis of a reaction of functional component.   25. Support according to one of claims 17 and 24, characterized in that the functional component nel is polymerizable under the influence of different kinds of energy.   26. Support according to one of claims 17 and 24, characterized in that the functional component is depolymerizable under the influence of different kinds of energy.   27. Support according to one of claims 16 and 20, characterized in that the degree of vaporization is modifiable on the basis of a reaction of said dye sprayable.   28. Support according to one of the claims   16 and 20, characterized in that the vaporizable dye   is a dye that can be sublimated.