JP2811386B2 - Image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a multicolor image by a dry development method. The method of the present invention is a method for obtaining a color proof directly from a digital image signal by laser recording (Direct Digital C).
color Proof: DDCP), and is particularly useful for producing a multicolor display.

[0002]

2. Description of the Related Art In the field of graphic arts, printing plate printing is performed using a set of color separation films from a color original. Before performing actual printing, a color proof is created from the color separation films and color printing is performed. An error check in the disassembly process, a necessity check of color correction, and the like are generally performed. As a material for this color proof,
It is considered that a pigment is preferably used as a coloring material together with image formation on printing paper, because of high similarity with printed matter.
Further, in addition to high resolution and high process stability that enable high reproducibility of halftone images, in recent years, a dry proofing method that does not use a developer has been required.

As a conventional color printing proofing method,
There is a method of performing proof printing using a print proofing machine and performing color proofing. However, this method is laborious and time-consuming, requires a high degree of skill, and has a limited reliability.

On the other hand, instead of these printing methods, various proofing methods using a photographic method have been developed as a simpler and easier method. Among these color proofing methods using a photographic method, there is a color proofing method using a photopolymer (prepress proof), which is widely used.

[0005] In the case of a photopolymerization system, which is a typical system of a photopolymer, many methods described below have been put to practical use for a conventional process in which exposure is performed using a photographic intermediate film as a mask. In order to obtain a high-quality color proof, it is generally necessary to reproduce a halftone image of 150 lines / inch or more, but this method basically has sufficiently high resolution. Also, many of the conventional photopolymerization initiators are sensitive to the near ultraviolet region, while
As disclosed in JP-A-54-155292, a number of spectral sensitizers for extending the photosensitive wavelength range to the visible range have been developed so far. Therefore, argon ion laser,
It is relatively easy to realize high recording sensitivity with respect to a laser having a visible light wavelength such as a helium-cadmium laser.

[0006] Here, due to the recent spread of the digitization system in the pre-printing process (pre-press field) and the demand for shortening the process and reducing the amount of consumables such as films, it is not necessary to pass through an intermediate material such as a lith film. There is an increasing demand for materials and recording systems that create color proofs directly from digital image signals. Therefore, in order to record a proof of high image quality from a digital signal, it is preferable to use a laser beam which can be modulated by the digital signal and can narrow down the recording light as a recording head. Therefore, the recording material is required to have high resolving power capable of reproducing halftone dots and high recording sensitivity to laser light. However, an essential problem is that a material capable of directly recording a digital signal and having practically usable quality has not yet been developed.

Although the above-described photopolymerization system has a high potential for digital image recording in terms of resolution and laser recording sensitivity, it has not been practically used yet. The following is an overview of the prior art of multicolor image recording by a photographic method using a photopolymerizable material, and points out problems in light of the object of the present invention.

As a conventional proofing method of color printing by a photographic method, there are an overlay method and a surprint method. The overlay method is a method of preparing a plurality of color proofing sheets on which a separation image of each color is provided on a transparent support, and performing proofreading by superimposing these sheets (the obtained one is referred to as a color test sheet). It is.

This overlay method is simple and inexpensive,
Each time only two or three colors are overlapped, which has the advantage that it can be used for continuous inspection. However, the color test sheet becomes slightly dark due to the overlapped synthetic resin sheet,
Also, the incident light is reflected from some sheets to give gloss,
Therefore, the impression received from the color test sheet has a drawback that is very different from that of the printed matter by the printing press.

On the other hand, surprinting involves the superposition of several colored images on a single support by providing various colored layers on a single opaque base or by a corresponding toner. Are sequentially provided on an opaque base. This superposition method has the advantage that the color density is not affected by the synthetic resin base, and has the unique advantage that it is easy to use a pigment that is the same as or similar in hue to the pigment used in the printing ink as a coloring material. Also,
It has become widely used.

As an example of this method, a photosensitive transfer material, in which a release layer made of an organic polymer, a color material layer and a photosensitive layer are sequentially laminated on a temporary support, is imagewise exposed and then wet-developed. Thus, a method is known in which a colored image is formed on the release layer, and then this colored image is transferred together with the release layer to an arbitrary support (permanent support) using an adhesive (Japanese Patent Publication No. 46-19764). No. 15326, Special Publication No. 49-44
No. 1). This method has an advantage that it can be used for various operations such as an overlay type and a surprint type as a color proof, but in order to sequentially transfer each color on a paper support having poor dimensional stability, It is difficult to maintain the alignment accuracy of each color, and the resulting image has weak mechanical strength.

As a method of improving the above-mentioned disadvantage, a method of temporarily transferring an image to a temporary image receiving sheet (image receiving element) before transferring the image onto a permanent support is disclosed in Japanese Patent Application Laid-Open No. H10-157, filed by the present applicant. No. 59-97140. That is, in this method, a temporary image-receiving element provided with an image-receiving layer made of a photopolymerizable material on a support is prepared, and the image of each color is temporarily transferred onto the temporary image-receiving element before the image is transferred onto the permanent support. The image of each color is transferred to the printer. Next, a step of re-transferring the image onto the permanent support, followed by further exposing the entire surface to cure the transferred photopolymerizable image receiving layer is included. According to this method, since the alignment and transfer of each color image can be performed on a support such as polyethylene terephthalate having high dimensional stability, both the alignment accuracy and the quality stability are improved, and the hardness is improved. Since the final image is protected by the large photo-cured layer, it also has the advantage of excellent mechanical strength of the image.

However, this method has an essential problem of a wet development method in principle. Further, from the viewpoint of laser recording suitability, if a dye sensitizer that spectrally sensitizes from the visible region to the infrared region is used, it is possible to record in principle, but the photosensitive layer and the color material layer can be used. Since they are the same or in contact with each other and are both transferred to the image receiving layer, the hue of the obtained image is greatly changed due to the coloring sensitizer, and thus has a problem that it cannot be put to practical use.

Many multicolor image forming methods which solve the disadvantages of the wet developing method found in the above-mentioned methods have been proposed in the past, and some of them have been widely put to practical use. Examples thereof are known from U.S. Pat. Nos. 3,060,024, 3,582,327, 3,620,726, and the like. In these methods, a support layer and at least one addition polymer are added. A tacky photopolymerizable replica material, consisting of a photopolymerizable layer containing a polymerizable monomer and a photopolymerization initiator, is cured by imagewise exposure and loses its tackiness. This latent image is then visualized by applying a suitable powdered toner material. The toner adheres only to the unexposed tacky areas, but can be removed from the exposed non-tacky image areas after application. This method is a dry development method that does not require a developing solution, and is widely used for proof printing using a color separation film because of its simplicity. However, since the powdery toner is handled, the surroundings of the work are easily stained, and the method of applying / removing the toner is likely to vary among individuals, and improvement is strongly desired.

As a method for improving the method using the adhesive photopolymerizable photosensitive layer, a method of forming a toner into a film is disclosed in, for example, JP-A-63-41847 and JP-A-Hei.
No. 14985. In these methods, similarly to the above method, a photosensitive layer which exhibits tackiness in an unexposed state and loses tackiness upon exposure / curing comprises a photopolymerizable monomer and a photoinitiator. Used in a form laminated on a receiver base such as paper. The latent image exposed by imagewise exposure and peeling of the photosensitive layer support is brought into contact with a film-like toner provided on another support, and the toner is transferred by being heated and / or pressed, Developed. Of the above two publications, the former is characterized by mixing polymers incompatible with each other as a binder for the toner layer, and the latter is also to select the thermal and mechanical properties of the binder polymer of the toner layer. As a result, the obtained image quality is improved. Both of these methods improve the drawbacks of the above-described method using a powder toner, and are excellent in the similarity of a printed matter (pigment image formation on printing paper), can be dry-developed, and have stable quality. Can be said to be a remarkably preferable method as compared with the conventional method.

However, there is still a problem to be solved in the method using the toner formed into a film. First, since the alignment of the image exposure of the photosensitive layer is repeated on a paper support having poor dimensional stability, misregistration of each hue image is likely to occur. Also, the final image has low mechanical strength, so if you want to have scratch resistance, adhesion resistance, etc.,
It was necessary to add a complicated process such as lamination of a protective layer on the final image. Further, there are problems that the resolution and halftone dot reproducibility of the final image are insufficient, the film strength of the toner film is low, and the toner film is easily damaged during handling.

[0017]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming method capable of easily and stably forming a high-quality image excellent in resolving power and dot reproducibility in a dry system. is there. Another object of the present invention is to provide an image forming method for directly forming a high-quality color proof with high print similarity by using a laser beam modulated by a digital image signal.

[0018]

Means for Solving the Problems The first present invention (hereinafter sometimes referred to as the first invention) comprises (A) adhesiveness to actinic rays when not exposed and non-adhesiveness after exposure. A step of forming a latent image by imagewise exposing the photosensitive layer of the photosensitive element having the photosensitive layer on the support (a) to actinic light, (B) forming a color material and The toner layer of the toner element having the toner layer containing the binder on the support (b)
(C) separating the toner element from the photosensitive element, transferring a portion of the toner layer corresponding to a non-exposed portion of the photosensitive layer onto the photosensitive layer, and In a method for forming an image comprising a toner layer on a support (b) by leaving a corresponding portion of the toner layer on the support (b), the binder may be 20%.
An image forming method comprising a thermoplastic resin containing polyvinyl butyral having a number average polymerization degree in a range of 0 to 800 and a butyralization degree in a range of 50 to 85% by weight as a main component.

The second invention (hereinafter sometimes referred to as the second invention) comprises (A) a photosensitive layer which exhibits tackiness when exposed to actinic light and is non-adhesive after exposure to a support ( a) a step of imagewise exposing an actinic ray to the photosensitive layer of the photosensitive element provided thereon to form a latent image, and (B) a toner layer containing a colorant and a binder in the photosensitive layer having the latent image formed thereon. Contacting the toner layer of the toner element on the support (b) in a face-to-face relationship; (C) separating the toner element from the photosensitive element to form a toner layer corresponding to a non-exposed portion of the photosensitive layer Is transferred onto the photosensitive layer, and the portion of the toner layer corresponding to the exposed portion of the photosensitive layer is left on the support (b) to form an image comprising the toner layer on the support (b). And (D) an image-receiving layer having an adhesive surface on a support (c). An image receiving layer of an image receiving element, the toner element is separated from the image receiving element, and the toner layer on which an image is formed is transferred to the image receiving element. The binder is 200
Number average degree of polymerization in the range of ~ 800 and 50-85% by weight
Is a thermoplastic resin containing, as a main component, polyvinyl butyral having a degree of butyralization within the range described above.

The third invention (hereinafter sometimes referred to as the third invention) comprises (A) a photosensitive layer which exhibits tackiness when exposed to actinic light when exposed to light and exhibits non-adhesion after exposure to a support ( a) a step of imagewise exposing an actinic ray to the photosensitive layer of the photosensitive element provided thereon to form a latent image, and (B) a toner layer containing a colorant and a binder in the photosensitive layer having the latent image formed thereon. Contacting the toner layer of the toner element with the toner element on the support (b) in a face-to-face relationship; and (C) separating the toner element from the photosensitive element to form a toner corresponding to an unexposed portion of the photosensitive layer. The portion of the layer is transferred onto the photosensitive layer, and the portion of the toner layer corresponding to the exposed portion of the photosensitive layer is left on the support (b) to form the support (b)
The step of forming an image composed of a toner layer thereon is performed for each of two or more types of toner elements having different hues, and then (D) supporting the image-formed toner layer on an image-receiving layer having an adhesive surface. After contacting the image receiving layer of the image receiving element on the body (c) in a face-to-face relationship, separating the toner element from the image receiving element, and transferring the toner layer on which the image has been formed to the image receiving element; In an image forming method comprising sequentially and repeatedly forming a multicolor image with two or more kinds of toner elements having different hues and one image receiving element, the binder may have a number average polymerization in a range of 200 to 800. Degree and 5
An image forming method, wherein the thermoplastic resin contains polyvinyl butyral having a butyral degree within a range of 0 to 85% by weight as a main component.

Preferred embodiments of the image forming method of the present invention are as follows. (1) After the step (D), the toner layer of the image receiving element to which the toner layer on which the image has been formed is transferred is brought into contact with the final image support while heating and / or pressing. And a step (E) of transferring the toner layer on the image receiving element onto the final image support by separating the image receiving element and the final image support from each other, and then adding the step (E). Or the image forming method of the third invention.

(2) The image forming method as described above, wherein the imagewise exposure of the photosensitive layer with actinic light is carried out by focusing and scanning a laser beam on the photosensitive layer.

(3) The above laser light is emitted from an argon ion laser, a helium neon laser, a helium cadmium laser, a dye laser, a semiconductor laser, a YAG laser, an excimer laser, or a second harmonic. The image forming method as described above, wherein the light is converted into a half wavelength by the element.

(4) The above-described image forming method, wherein the toner layer further contains a plasticizer.

(5) The plasticizer contained in the toner layer comprises one or more plasticizers selected from phosphoric esters, acrylic esters, polyol esters and epoxy compounds. Image forming method.

(6) The photosensitive layer comprises a photopolymerizable monomer and / or
Alternatively, the above-described image forming method containing at least an oligomer, an organic polymer binder, and a photopolymerization initiator.

(7) The above-described image forming method wherein the photosensitive layer exposed to actinic rays is heated and / or pressed when the photosensitive layer is brought into contact with the toner layer in a face-to-face relationship.

(8) When the toner layer remaining on the toner element corresponding to the image-like pattern by the actinic light exposure is brought into face-to-face contact with the image receiving element, the toner layer and / or the image receiving element are contacted. The above-described multicolor image forming method in which heating and / or pressing are performed.

The present invention will be described in detail with reference to the accompanying drawings.

First, the first invention will be described. FIG. 1 is a sectional view schematically showing a section of an example of the photosensitive element used in the first invention. In FIG. 1, a photosensitive element 11 is configured by providing a photosensitive layer 13 on a support (a) 12.

The support (a) 12 is not particularly limited as long as it is in the form of a film or a plate, and may be made of any substance. Examples of the material of the support (a) 12 generally include, for example, polymer compounds such as polyethylene terephthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer. In particular, biaxially stretched polyethylene terephthalate is preferred in terms of mechanical strength and dimensional stability against heat. The thickness of the support (a) 12 is generally from 10 to 400 μm, particularly preferably from 25 to 200 μm in the case of a film. In some applications, the support (a) 1
As glass 2, a metal plate or the like can be used. Further, either the support (a) 12 or a cover sheet described later needs to be in the form of a film, and is preferably transparent to actinic rays.

On the surface of the support (a) 12 on the photosensitive layer 13 side, an intermediate layer may be laminated or a physical surface treatment may be applied in order to increase the adhesion to the photosensitive layer 13. As the intermediate layer, a polymer material having a film property is used to determine the adhesion between the support (a) 12 and the photosensitive layer 13 and the solubility in a solvent in the photosensitive layer forming composition when the photosensitive layer 13 is applied. It is appropriately selected in consideration of the above. The thickness is not particularly limited, but is usually preferably 0.01 μm to 2 μm. As means for increasing the adhesion, physical treatments such as glow discharge treatment and corona discharge treatment on the surface of the support (a) 12 may be used.
Particularly preferred.

The photosensitive layer 13 may be made of any of various materials as long as they exhibit tackiness in an unexposed state to actinic rays and a non-adhesive state in an exposed state. As an example of such a material, a system in which a photosensitive compound such as vinyl cinnamate or a photosensitive azide compound is blended with a polymer may be used, but the most preferable system in terms of light sensitivity and the like is a photopolymerizable photosensitive material. It is.

Suitable photopolymerizable photosensitive materials for use in the photosensitive layer 13 include: i) at least one photopolymerizable monomer and / or oligomer capable of forming a photopolymer by addition polymerization; ii) at least one organic polymer. A coalescing binder (polymer binder); and iii) at least one actinic light-activated photopolymerization initiator, and if necessary, further additives such as a thermal polymerization inhibitor and a surfactant. I do.

The above photopolymerizable monomers and oligomers (hereinafter simply referred to as “photopolymerizable monomers” including oligomers)
Is not particularly limited as long as it can form a photopolymer by addition polymerization, but is preferably a polyfunctional vinyl or vinylidene compound. Suitable as polyfunctional vinyl or vinylidene compounds are
For example, unsaturated esters of polyols, especially esters of acrylic acid or methacrylic acid, such as ethylene glycol diacrylate, glycerin triacrylate, ethylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, polyethylene glycol dimethacrylate, 1, 2, 4, Butanetriol trimethacrylate, trimethylolethane triacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta Erythrit polyacrylate, 1,3-propanediol diacrylate, 1,5-pentane Diol over dimethacrylate, 2
Bisacrylates and bis-methacrylates of polyethylene glycol having a molecular weight of 00 to 400 and similar compounds, unsaturated amides, in particular of acrylic and methacrylic acids having an α, ω-diamine whose alkylene chain may be opened by a carbon atom Unsaturated amide and ethylene bis-methacrylamide. Further, for example, polyester acrylate obtained by condensation of an ester of a polyhydric alcohol and a polyhydric organic acid with acrylic acid or methacrylic acid may be used, but is not limited thereto.

The above-mentioned organic polymer binder is one of the major factors that determine not only the hardness of the photosensitive layer 13 but also its tackiness. Suitable materials for the above binder are thermoplastic resins or mixtures thereof, for example, homopolymers or copolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylates, methacrylates and the like. Coalesce, methylcellulose, ethylcellulose, cellulosic polymers such as cellulose acetate, polystyrene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl polymers such as polyvinylpyrrolidone, polyvinylbutyral, polyvinyl alcohol and the like, and copolymers thereof. Examples thereof include condensed polymers such as coalesced polyesters and polyamides, chlorinated rubbers, rubber polymers such as butadiene-styrene copolymers, and polyolefin polymers such as chlorinated polyethylene and chlorinated polypropylene. Among them, copolymers of various acrylic monomers are preferable because they can easily control thermal properties such as softening point in a wide range and have good compatibility with photopolymerizable monomers. These polymers, 10, 000-2, it preferably has an average molecular weight of 000, 000. Here, the mixing ratio between the photopolymerizable monomer and the organic polymer binder has an appropriate ratio depending on the combination of the photopolymerizable monomer and the binder used. The ratio is preferably 0.1: 1.0 to 2.0: 1.0 (weight ratio).

As the above-mentioned photopolymerization initiator, it is particularly preferable to use a photopolymerization initiator having absorption and activity at a longer wavelength than the visible region and having high photosensitivity to laser. As such a photopolymerization initiator, many systems in which a radical generator and various dyes as spectral sensitizers are combined are known. For example, an imidazole dimer is used as a radical generator, and an acridine dye (JP-A-5
4-155292), triazine dyes (TAGA
Proceedings, 1985, p. 232), N-phenylglycine as a radical generator, and a ketocoumarin-based (Polymer Eng. Sc) as a pigment.
i. , 23, 1022 (1983)), a system in which various dyes are combined using an iodonium salt as a radical generator (JP-A-60-76740, JP-A-60-78443, JP-A-60-88005, etc.), and a triazine-based compound as a radical initiator As compounds and dyes, aromatic ketone derivatives (Journal of the Chemical Society of Japan, 1984, p. 192) and the like are known. Alkyl borate salts of dyes such as cyanine, rhodamine and safranine are also known as effective visible light initiators (JP-A-62-143044 and JP-A-62-150242).
In the first invention, these known photopolymerization initiator systems can be used.

The photosensitive layer 13 absorbs near-ultraviolet light,
Initiators having activity can be used alone or in combination with the above-mentioned initiators depending on the use and purpose. Benzophenone, an initiator having near-ultraviolet absorption and activity
Michler's ketone [4,4'-bis- (dimethylamino)
Benzophenone, 4,4'-bis - (diethylcarbamoyl Ruami <br/> Roh) benzophenone, 4-methoxy-4'-dimethylamino benzophenone, 2-ethylanthraquinone, acetophenone tiger quinones, and as other aromatic ketones Aromatic ketones, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin ethers such as benzoin phenyl ether, methyl benzoin, ethyl benzoin and other benzoins, and 2- (o-chlorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,
5- (m-methoxyphenyl) imidazole dimer, 2
-(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,
5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5 diphenylimidazole dimer,
2,4-di (p-methoxyphenyl) -4,5 diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5 diphenylimidazole dimer, and U.S. Pat. No. 3,476,185 , UK Patent No. 1,04
2,4,5-Triacrylimidazole dimers and the like, such as similar dimers in US Pat. Nos. 7,569 and 3,784,557 are used.

The addition amount of the photopolymerization initiator is preferably from 0.01 to 30% by weight based on the photopolymerizable monomer.

In the photosensitive layer 13, a thermal polymerization inhibitor can be added. Examples of this include, but are not limited to, p-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, tert-butyl catechol, pyrogallol, naphthylamine, β-naphthol, phenothiazine, pyridine, nitrobenzene, φ-tolutinone, aryl phosphite, and the like. Not something.

Further, in the photosensitive layer 13, it is also possible to add a printing-out agent which forms a visible color image upon exposure to imagewise actinic light, and its material is as follows.
It is used by selecting from known ones. Other components that can be added to the photosensitive layer 13 include a plasticizer, a residual solvent,
Surfactants, inert fillers and the like.

The photosensitive layer 13 is prepared by applying a coating solution for forming the photosensitive layer 13 containing the above components on the support (a) 12 (or the intermediate layer) according to a known coating film forming method. Can be formed by drying. The thickness of the photosensitive layer 13 is preferably in the range of about 0.1 μm to 100 μm, and more preferably in the range of about 1 μm to 50 μm.

Although not shown in FIG. 1, the photosensitive layer 13 has a surface on the side opposite to the support (a) 12 for protecting the photosensitive layer 13 before recording and for preventing oxygen in the air during exposure. It is preferable to provide a cover film in order to reduce the polymerization inhibiting effect of the polymer. The material of the cover film is generally, for example, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-acrylonitrile copolymer and other high-molecular compounds, particularly, Polyethylene, polypropylene and polyethylene terephthalate are preferred. The thickness of the cover film is generally 5 to 400 μm, particularly 10 to 200 μm.
m is preferable.

A release layer made of a silicone resin or the like may be provided on the surface of the cover film which is in contact with the photosensitive layer 13 in order to reduce the adhesion to the photosensitive layer 13. The thickness is not particularly limited, but is usually preferably 0.01 μm to 2 μm.

In the first invention, first, in the step (A), a latent image is formed by exposing actinic rays imagewise to the photosensitive layer 13 of the photosensitive element 11 configured as described above. Ultraviolet rays such as a mercury lamp and a xenon lamp, a laser beam and the like can be used as the actinic ray. When ultraviolet light is used, the entire surface is irradiated through an image mask. When laser light is used, laser light modulated by an image signal is focused on the photosensitive layer 13 to an appropriate beam diameter and scanned. Exposure can be performed as follows.
It is preferable to use laser light as the actinic light, since imagewise exposure can be performed directly using digital data from the image processing system.

The laser light may be a gas laser such as an argon ion laser, a helium neon laser, a helium cadmium laser, a solid laser such as a YAG laser, a semiconductor laser, or a light directly emitted from a dye laser, an excimer laser, or the like. Alternatively, it is possible to use light obtained by converting the emitted light to a half wavelength through a second harmonic element. The laser is appropriately selected from these lasers according to the photosensitive wavelength, sensitivity, and required recording speed of the photosensitive layer 13. Modulation of laser light by an image signal is known, for example, in the case of an argon ion laser, a beam is passed through an external modulator, and in the case of a semiconductor laser, the current injected into the laser is controlled (directly modulated) by a signal. It is carried out by the method described below. Also,
Focusing the modulated laser light on the photosensitive layer and scanning the same are also performed by a known method. Laser light can be incident from either the support (a) side or the cover film side. In order to scan with laser light,
In general, a method of rotating a photosensitive element on a rotating drum at a high speed and moving (sub-scanning) a laser beam while synchronizing in a direction orthogonal to the scanning direction (drum scanning method); There is a method of moving the photosensitive element in the orthogonal direction (sub-scanning) while scanning the photosensitive element with a laser beam at high speed (planar scanning method). In the first invention, any of these methods or their modified methods can be used.

FIG. 2 is a cross-sectional view schematically showing a state of the photosensitive layer when the photosensitive layer of the photosensitive element is imagewise exposed to actinic rays in the first invention. In FIG. 2, the photosensitive layer 13 on the support (a) 12 of the photosensitive element 11 after being imagewise exposed to the actinic ray AL has an unexposed area 13Y which is not exposed to the actinic ray AL, and remains unchanged. 13X exposed by the actinic ray AL
Have changed to show non-stickiness (lack of stickiness). Exposure with the actinic light LA in this way allows the photosensitive layer 1 to be exposed between the exposed area 13X and the unexposed area 13Y.
3, a latent image is formed.

In the first invention, next, in the step (B), the toner layer of the toner element used in the first invention is added to the photosensitive layer on which the latent image obtained in the step (A) is formed. The surface-
Contact in face-to-face relationship.

FIG. 3 is a cross-sectional view schematically showing a state in which an example of a photosensitive element having a latent image formed on the photosensitive layer in step (B) of the first invention is in contact with an example of a toner element. In FIG. 3, a photosensitive element 11 is the same as the photosensitive element 11 shown in FIG. 2, and a photosensitive layer 13 formed on a support (a) 12 of the photosensitive element 11 has an exposed area 13X and an unexposed area. An exposure area 13Y is formed. Further, the toner element 21
A toner layer 23 is provided on a support (b) 22. The photosensitive layer 13 and the toner layer 23 are in contact in a face-to-face relationship.

The toner element 21 will be described in detail.
The support (b) 22 is not particularly limited as long as it is in the form of a film, and may be made of any substance. Examples of the material of the support (b) 22 generally include, for example, polymer compounds such as polyethylene terephthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer. In particular, biaxially stretched polyethylene terephthalate is preferred in terms of mechanical strength and dimensional stability against heat. The thickness of the support (b) 22 is generally 5 to 400 μm, particularly 10 to 100 μm.
It is preferred that

Although not shown in FIG. 3, the support (b)
If necessary, the surface of the toner layer 22 on the side of the toner layer 23 may be subjected to lamination of an intermediate layer or physical surface treatment for the purpose of reducing or increasing the adhesion to the toner layer 23. As the intermediate layer, in consideration of adhesion to the toner layer 23 and solubility in a solvent when the toner layer 23 is applied,
It is appropriately selected from materials having a coating property. In order to lower the adhesion to the toner layer 23, a silicone resin such as poly (dimethylsiloxane), a water-soluble polymer such as gelatin, and polyvinyl alcohol are used. The thickness is not particularly limited, but is usually preferably 0.01 μm to 5 μm. As means for increasing the adhesion to the toner layer 23, physical treatment such as glow discharge treatment and corona discharge treatment on the surface of the support (b) 22 is also particularly preferable.

The toner layer 23 contains at least one kind of coloring material and binder. In general, the toner layer 23 is formed by dissolving and / or dispersing a colorant, a binder, and, if necessary, a toner layer forming component in a solvent in a solvent, using a known method. Is formed on the surface of the support (b) 22 by applying and drying.

As a coloring material contained in the toner layer 23, a pigment or a dye is used. Pigments are generally classified into organic pigments and inorganic pigments. The former has excellent transparency of the coating film, and the latter generally has excellent concealing properties. When used for printing color proofing, organic pigments having a color tone that matches or is close to yellow, magenta, cyan, and black used in printing inks are preferably used. In addition, metal powders, fluorescent pigments and the like are also used according to the purpose. Pigments suitably used include azo-based, phthalocyanine-based, anthraquinone-based, etc., slene-based, dioxazine-based, quinacridone-based, and isoindolinone-based pigments.

The pigment is typically dispersed together with an organic binder in an organic solvent or an aqueous dispersion medium. The pigment is ground to an extent that reproduces the color and image quality of the corresponding image. Generally, an average particle size of 1 micron or less is preferred.

The following examples are just a few of the many pigments and dyes known in the art (CI stands for color index). Victoria Pure Blue (CI. 42593) Auramine O (CI. 41000) Katilon Brilliant Flavin (CI. Basic 1)
3) Rhodamine 6GCP (C.I. 45160) Rhodamine B (C.I. 45170) Safranin OK70: 100 (C.I. 50240) Erioglaucine X (C.I. 42080) First black HB (C.I. 26150) No. 1201 Lionol Yellow (CI. 2109)
0) Lionol Yellow GRO (CI. 21090) Shimla First Yellow 8GF (CI. 2110)
5) Benzidine Yellow 4T-564D (CI. 2109)
5) Shimura Fast Red 4015 (CI. 1235)
5) Lionol Red 7B4401 (CI. 15850) Fastgen Blue-TGR-L (CI. 7416)
0) Lionol Blue SM (CI. 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black # 40

In addition to these pigments, Ciba Geigy Co., Ltd.
Processed pigments obtained by dispersing a fine particle pigment in a polymer carrier manufactured and sold by, for example, Microlith Yellow 4GA and Microlith Yellow 2R-A (CI.2).
1108), Microlith Yellow MX-A (CI.2)
1100), Microlith Blue 4G-A (CI.74)
160), Micro Red Red 3R-A, Micro Red Red 2CA, Micro Red Red 2BA, Micro Lith Black CA and the like are also used.

The binder contained in the toner layer 23 is 200
Number average degree of polymerization in the range of ~ 800 and 50-85% by weight
Is a thermoplastic resin containing, as a main component, polyvinyl butyral having a degree of butyralization within the range. Polyvinyl butyral is a known polymer, adhesive, paint,
It is used for applications such as ceramic binders.For example, polyvinyl alcohol generally produced by hydrolyzing polyvinyl acetate is reacted with butyraldehyde using an acid catalyst, and is produced by acetalizing a hydroxyl group. . Various polyvinyl butyral having a number-average degree of polymerization and a degree of butyralization that can be varied over a wide range can be produced, but the polyvinyl butyral used as a binder in the toner layer of the toner element in the first invention is 20%.
A limitation having a number average degree of polymerization in the range of 0-800, preferably in the range of 200-400, and a degree of butyralization in the range of 50-85% by weight, preferably in the range of 65-80% by weight. Polyvinyl butyral.
When the number average degree of polymerization of the polyvinyl butyral is smaller than the above range, the film strength (scratch resistance) of the toner layer is reduced, and the image quality is deteriorated. When the number average degree of polymerization is larger than the above range, it is formed. Poor image resolution and halftone dot reproducibility. Further, when the butyral degree of the polyvinyl butyral is smaller than the above range, the resolution and halftone dot reproducibility of an image to be formed are inferior, storage stability is reduced, and when the butyral degree is larger than the above range, the image quality is reduced. , And the material cost increases, which is industrially disadvantageous.

The binder contained in the toner layer 23 is a thermoplastic resin containing at least 50% by weight, preferably at least 70% by weight, more preferably at least 85% by weight of the polyvinyl butyral as described above. The binder contained in the toner layer 23 includes, in addition to the polyvinyl butyral as described above,
Methylcellulose, ethylcellulose, cellulose derivatives such as cellulose triacetate, homopolymers or copolymers of acrylic monomers such as acrylic acid, methacrylic acid, acrylates, methacrylates, etc., styrene / maleic anhydride resins and the like An organic polymer such as a half ester may be contained.

In the toner layer 23, the binder functions to control the rheological properties of the toner layer 23 and to stabilize the dispersed pigment.

The mixing ratio of the colorant and the binder in the toner layer 23 varies depending on the combination of the colorant and the binder, but generally the colorant: binder ratio is 100: 30 to 100: 30.
It is preferably 0 (weight ratio).

The toner layer 23 is not essential, but improves the adhesion between toner layers of different hues.
A plasticizer can be added to promote transfer to the image receiving element. The plasticizer to be used is appropriately selected depending on the combination with the coloring material and the binder. Examples of plasticizers include
Dibutyl phthalate (DBP), di-n-octyl phthalate (DnOP), di (2-ethylhexyl) phthalate
(DOP), dinonyl phthalate (DNP), dilauryl phthalate (DLP), butyl lauryl phthalate (BL)
P), phthalic esters such as butylbenzyl phthalate (BBP), di (2-ethylhexyl) adipate (D
OA), di (2-ethylhexyl) sebacate (DO
S) and other aliphatic dibasic acid esters, tricresyl phosphate (TCP), tri (2-ethylhexyl) phosphate (TO
Examples include, but are not limited to, phosphoric acid triesters such as P), polyol esters such as polyethylene glycol ester, and epoxy compounds such as epoxy fatty acid esters.

In addition to the above general plasticizers, polyethylene glycol dimethacrylate, 1,2,4 butanetriol trimethacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta Acrylic esters such as erythritol polyacrylate are also suitably used depending on the type of the binder.
These plasticizers may be used alone or in combination of two or more. A secondary plasticizer (auxiliary plasticizer) such as polychlorinated paraffin may be blended with these plasticizers.

The amount of the plasticizer to be added varies depending on the combination of the coloring material and the binder. In general, the weight ratio of (total amount of the coloring material and the binder): plasticizer is 100: 1 to 10.
0: 200, particularly preferably 100: 2 to 100: 100.

In addition to the components described above, a toner layer 23
May further contain a surfactant, a thickener, a dispersion stabilizer, an adhesion promoter, and other additives.

The toner layer 23 can be formed with the above-mentioned coloring material, binder, and if necessary, other components such as a plasticizer to obtain a desired particle size and color by a known coating film forming method. The obtained paste is diluted with a solvent or a solvent mixture, and the coating liquid for forming the toner layer 23 obtained as a dispersion having a desired viscosity is coated on the support (b) 22. It can be formed by coating and drying. The dry film thickness of the toner layer 23 depends on the intended use, but generally does not exceed 10 μm, and is preferably 0.1 μm to 4 μm.

Although not shown in FIG. 3, the toner layer 23
If necessary, a cover film may be provided on the surface of the device to prevent scratches during handling and prevent adhesion between membrane surfaces during storage. As a material of the cover film for these purposes, for example, generally, polyethylene terephthalate, polycarbonate, polyethylene,
Examples include high molecular compounds such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer, and polyethylene, polypropylene and polyethylene terephthalate are particularly preferable. The thickness of the cover film is generally 5 to
It is preferably 400 μm, particularly preferably 10 to 100 μm. The surface of the cover film which comes into contact with the toner layer 23 may be subjected to the same treatment as the surface treatment of the cover film of the photosensitive layer 13 in order to control the adhesiveness of the cover film.

In the first invention, in the step (B), as shown in FIG. 3, a toner element is formed on the photosensitive layer 13 of the photosensitive element 11 on which the latent image obtained in the step (A) is formed. The 21 toner layers 23 are brought into contact in a face-to-face relationship. The contact between the photosensitive layer 13 and the toner layer 23 is preferably performed under heat and / or pressure. The temperature is generally between room temperature and 16
The temperature is preferably 0 ° C, particularly room temperature to 130 ° C, and the pressure is generally 0.5 to 100 kg / cm ² (gauge pressure), particularly preferably 1 to 10 kg / cm ² (gauge pressure). Contact between the photosensitive layer 13 and the toner layer 23 is
Generally, it can be performed by passing the photosensitive element 11 and the toner element 21 through a laminator.

In the first invention, in the following step (C), the toner element 21 is separated from the photosensitive element 11. FIG. 4 is a cross-sectional view schematically showing a state where the toner element 21 is separated from the photosensitive element 11 in the step (C). In FIG. 4, the unexposed area 13Y of the photosensitive layer 13 of the photosensitive element 11 which is not exposed by the actinic ray AL remains unchanged and sticky, and the exposed area 13 which is exposed by the actinic ray AL.
Since X has changed to show non-adhesiveness (losing adhesiveness), the corresponding area 23Y of the toner layer 23 in contact with the unexposed area 13Y of the photosensitive layer 13 adheres to the unexposed area 13Y, The corresponding area 23X of the toner layer 23 that is in contact with the exposed area 13X of the photosensitive layer 13 does not adhere to the exposed area 13X and remains on the support (b) 22. As a result, an image of the toner layer portion 23Y corresponding to the unexposed area 13Y is formed on the photosensitive layer 13, while the toner layer portion corresponding to the exposed area 13X of the photosensitive layer 13 is formed on the support (b) 22. A 23X image is formed.

In the first invention, since the toner element having the toner layer containing the specific binder is used as described above, the toner layer 23 is brought into contact with the photosensitive layer 13 in a face-to-face relationship. After the image formation, the separation of the toner layer from the exposed area of the imagewise exposed photosensitive layer and the adhesion of the toner layer to the unexposed area of the photosensitive layer are reliably performed. The toner layer remaining on the photosensitive layer faithfully corresponds to the exposed area of the photosensitive layer. As a result, a high-quality image with excellent resolution and halftone dot reproducibility is stably formed on the support (b). It is done. As is clear from the above description, the image corresponding to the unexposed area formed on the photosensitive element at the same time is of high quality.

Next, the second invention will be described. The second invention relates to the first invention in which the toner layer on the support (b) obtained in the step (C) of the first invention, on which an image is formed, is formed by adding the image-receiving layer having an adhesive surface to the support (c). B) contacting the image receiving layer of the image receiving element with the image receiving layer in a face-to-face relationship, separating the toner element from the image receiving element, and transferring the toner layer on which an image has been formed to the image receiving layer of the image receiving element. ).

Accordingly, the steps (A), (B) and (C) in the second invention are the same as the steps (A), (B) and (C) in the first invention, respectively. And
In the step (C), a toner element is obtained in which an image composed of a portion of the toner layer corresponding to an exposure area of the photosensitive layer of the photosensitive element by actinic rays is formed on the support (b). Hereinafter, step (D) of the second invention will be described in detail.

FIG. 5 is a cross-sectional view schematically showing a state in which an example of the toner element on which the image obtained in the step (C) of the second invention has been formed is brought into contact with an example of the image receiving element. In FIG. 5, the toner element 21 is the same as the toner element 21 shown in FIG.
And the support (b) 22 of the toner element 21
On the upper side, an image of the toner layer portion 23X corresponding to the exposure region 13X of the photosensitive layer 13 shown in FIG. 4 is formed. The image receiving element 31 has an image receiving layer 3 on a support (c) 32.
3 are provided. Then, the toner layer 23
And the image receiving layer 33 are in contact in a face-to-face relationship.

The support (c) 32 is not particularly limited as long as it is in the form of a film or a plate, and may be made of any substance. As the material of the support (c) 32, generally, for example, high molecular compounds such as polyethylene terephthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer can be exemplified. In particular, biaxially stretched polyethylene terephthalate is preferred in view of dimensional stability against water and heat. The thickness of the support (c) 32 is generally 10 to 400 μm, preferably 25 to 200 μm in the case of a film. Further, depending on the application, glass, a metal plate, or the like can be used as the support (c) 32.

Although not shown in FIG. 5, the surface of the support (c) 32 may have been subjected to a lamination of an intermediate layer or a physically suitable surface treatment to enhance the adhesion to the image receiving layer 33. Good. The intermediate layer is appropriately selected from a polymer material having a film property in consideration of the adhesion to both the support and the image receiving layer. The thickness is not particularly limited, but is usually preferably 0.01 μm to 2 μm. As means for increasing the adhesion, a physical treatment such as a glow discharge treatment or a corona discharge treatment on the surface of the support is also particularly preferable.

The image receiving layer 33 has a softening temperature of about 8 by the Vicat method in order to receive the toner layer.
Polymer layers below 0 ° C. are preferred. Further, in order to transfer the image to the printing paper as needed, in order to obtain an appropriate release property, the material for forming the image receiving layer 33 is disclosed in JP-A-59-97.
It is preferably made of a photopolymerizable material as described in JP-A-140.

Particularly preferred as the image receiving layer 33 are: iv) at least one photopolymerizable monomer or oligomer capable of forming a photopolymer by addition polymerization; v) at least one organic polymer binder (polymer binder); ) At least one photopolymerization initiator, and vii) an additive such as a thermal polymerization inhibitor that is added as needed. Examples of the photopolymerizable monomer or oligomer include the same substances as the photopolymerizable monomer or oligomer used in the photosensitive layer 13, and examples of the organic polymer binder include:
The same substances as the organic polymer binder used in the photosensitive layer 13 can be used.

The above-mentioned photopolymerization initiator must be a compound having absorption and activity in the near ultraviolet region and no absorption in the visible region, or a small compound. Such examples include benzophenone, Michler's ketone [4,4'-bis- (dimethylamino) benzophenone], 4,4'-bis- (dimethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenonetraquinone And other aromatic ketones such as aromatic ketones, benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenethyl ether, methyl benzoin, ethyl benzoin and other benzoins, and 2- ( O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (O-chlorophenyl) -4,5- (m-methoxyphenyl) imidazole dimer, etc. And include photoinitiator having activity in the near ultraviolet.

Here, the mixing ratio of the photopolymerizable monomer and the organic polymer binder varies depending on the combination of the monomer compound and the binder used, but generally, the monomer: binder ratio is 0.1%. 1: 1.0-2.0: 1.0 (weight ratio) is preferred. The addition amount of the photopolymerization initiator is preferably 0.01 to 20% by weight based on the monomer compound.

The image receiving layer 33 is formed by applying a coating solution for forming an image receiving layer containing the above-mentioned components on the support (c) 32 and drying the coating solution according to a known coating film forming method. can do. The film thickness of the image receiving layer 33 needs to be deformed in order to receive the toner layer portion 23X. In general, 2 g / m ^{2 to} 50 g / m ² is preferable, though it depends on the thickness of the portion 23 </ b> X.

Although not shown in FIG. 5, the image receiving layer 33
May have a two-layer configuration as necessary. In particular, when the image on the image receiving layer 33 is transferred to a permanent support such as printing paper in a later step, a method of transferring the upper layer of the two layers together with the image and leaving the lower layer (support side) on the image receiving element is particularly featured. Kaisho 61
189535, JP-A-2-244146, 2-2
Nos. 44147 and 2-244148. The methods described in these publications are preferable from the viewpoint of similarity to printed matter and other points.
Is preferably a two-layer structure.

In the step (D) of the second invention, the contact between the toner layer 23 and the image receiving layer 33 is preferably performed under heat and / or pressure. The temperature is generally between room temperature and 160
° C., preferably in particular at room temperature to 130 DEG ° C., the pressure is generally 0.5~100kg / cm ² (gauge pressure), particularly preferably 1 to 10 kg / cm ² (gauge pressure). The contact between the toner layer 23 and the image receiving layer 33
Generally, it can be carried out by passing the support (b) 22 on which an image is formed and the image receiving element 31 through a laminator.

In the step (D) of the second invention, the toner element support (b) 22 is separated from the image receiving element 31. FIG. 6 is a cross-sectional view schematically showing a state where the support (b) 22 is separated from the image receiving element 31 in the step (D). In FIG. 6, a support (b) 2 is provided on the image receiving layer 33.
The image of the toner layer portion 23 </ b> X formed on the image receiving layer 2 is transferred, and an image is formed on the image receiving layer 33. Toner layer 23
The toner layer portion 23X is partially or entirely brought into contact with the image receiving layer 33 by heating and / or pressurizing the toner layer.
It will be embedded inside.

In the second invention, since the toner element having the toner layer containing the specific binder is used as described above, the toner layer 23 is brought into contact with the photosensitive layer 13 in a face-to-face relationship. After the image formation, the separation of the toner layer from the exposed area of the imagewise exposed photosensitive layer and the adhesion of the toner layer to the unexposed area of the photosensitive layer are reliably performed. 3) faithfully corresponds to the exposed area of the photosensitive layer, and the image formed on the support (b) of the toner element is reliably transferred to the image receiving layer. As a result, a high-quality image with excellent resolving power and dot reproducibility is stably formed on the image receiving element.

Next, the third invention will be described. In the third invention, the step (A), the step (B) and the step (C) of the second invention are performed for each of two or more kinds of toner elements having different hues, and the step (D) of the second invention is performed in the hue. (B) having a toner layer on which an image obtained in step (C) is formed for each of two or more kinds of toner elements having different
And a single image receiving element to sequentially form a multicolor image.

That is, the steps (A), (B) and (C) in the third invention are the same as the steps (A), (B) and (C) in the first invention, respectively. In the step (C), a toner element is obtained in which an image composed of a portion of the toner layer corresponding to an exposure area of the photosensitive layer of the photosensitive element by actinic rays is formed on the support (b). In the third invention, two or more kinds of toner elements having different hue of the toner layer are used, and the steps (A), (B) and (C) are performed for each toner element, and the toner of each hue is obtained. With respect to the element, a toner element is obtained in which an image composed of the toner layer is formed on the support (b). Then, the step (D) of the second invention in which the toner layer of the toner element having the image formed on the support (b) is transferred to the image receiving layer of the same image receiving element, the two or more kinds of toner having different hues are used. The multi-color image is formed by successively performing the elements and overlaying images having different hues on the image receiving layer. The step (D) in the third invention is the same as the step (D) in the second invention for each toner element.

In the third invention, two or more hues of the toner element are not particularly limited, but when a full-color multi-color image is formed, generally four hues, ie, yellow,
Magenta, cyan, and black colors are used. The hue of the toner element can be adjusted to a desired hue by adjusting the type and content of the coloring material contained in the toner layer.

In the third invention, first, an image for a specific hue AA (for example, yellow) obtained by color separation is exposed to a photosensitive layer in step (A). Next, the steps (B) and (C) are performed using a toner element having a hue AA corresponding to the color separation image. Thus hue AA
Is obtained. Step (D) is performed using the toner element AA to form an image of hue AA on the image receiving layer of the image receiving element.

Next, for a hue BB different from the hue AA, a toner element BB on which a hue BB image is formed is obtained in the same manner as described above except that a toner element having the hue BB is used. The step (D) is performed using the toner element BB and the image receiving element on which the image of the hue AA obtained as described above is formed, and the image of the hue BB is formed on the image receiving layer of the image receiving element. .

Next, the same process is performed for the hue CC different from the hue AA and the hue BB, and the hue CA is applied to the image receiving layer of the image receiving element on which the hue AA image and the hue BB image are formed.
The image of C is superposed and formed.

In the same manner as described above, a multicolor image can be formed on the image receiving layer of the image receiving element by performing the processing for other hues. By selecting yellow, magenta, cyan, and black as hues, a full-color image can be formed.

Formation (development) of separated images of each hue
Conditions to transfer and transfer conditions reduce errors in work,
From the viewpoint of increasing the processing efficiency, it is preferable that they are set to be the same.

FIG. 7 is a cross-sectional view schematically showing a state in which an image of hue AA and an image of hue BB are formed on the image receiving layer of the image receiving element according to the third invention. Image receiving layer 32 of image receiving element 31
Are formed with a toner layer portion 23AA of hue AA and a toner layer portion 23BB of hue BB.

In the second and third inventions, after the step (D), the toner layer portion of the image receiving element to which the toner layer on which the image has been formed is transferred is transferred to the final image support (for example, white paper). ) In a face-to-face contact with heat and / or pressure, and then separating the image receiving element and the final image support from each other so that the toner layer portion on the image receiving element is placed on the final image support. The step (E) of transferring can be performed. If the image receiving layer is photopolymerizable, the entire surface is exposed to ultraviolet light through the transparent support of the image receiving element to photo cure the image receiving layer. By peeling the transparent support,
A multicolor registered image transferred on white paper is obtained.

When the final image is transferred and formed on paper and used, when scanning and recording the laser beam on the photosensitive layer in the step (A), the original is viewed from the photosensitive layer (or cover film) side. Image opposite to left and right (reverse image)
It is necessary to scan and record so that

The image forming method of the present invention can be applied to various color displays, color mosaic patterns of color filters for liquid crystal displays,
It is useful for making wiring patterns for electronic circuits (using metal powder as a coloring material), medical images by computer output, and mask films such as lith films.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[Example 1] A coating solution for an intermediate layer having the following composition was prepared. Polymer: ethylene-ethyl acrylate copolymer 20 parts by weight (trade name: Eveflexs A-709, manufactured by Mitsui Petrochemical Co., Ltd.) Solvent (toluene) 100 parts by weight Polyethylene terephthalate (PE) having a thickness of 100 μm
T) Using the film as a support (a), the above-mentioned coating solution for an intermediate layer was applied at 200 rpm using a rotary coating machine (whiter).
m for 1 minute and dried in an oven at 100 ° C. for 2 minutes. The thickness of the obtained intermediate layer was 20 μm.

A coating solution for a photosensitive layer having the following composition was prepared. Binder (33% solution of benzyl methacrylate / methacrylic acid copolymer in methyl cellosolve acetate, copolymer composition = 67/33) 45.5 parts by weight Photopolymerizable monomer Tetraethylene glycol diacrylate 3.0 parts by weight Pentaerythritol tetra Acrylate 5.0 parts by weight Initiator A (Structural Formula A) 0.6 parts by weight

[0099]

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Surfactant (trade name: Florade FC-430, manufactured by Sumitomo 3M Ltd.) 0.1 part by weight Methyl ethyl ketone 110 parts by weight Propylene glycol monomethyl ether acetate 55 parts by weight On the above-mentioned intermediate layer, on the above-mentioned photosensitive layer Coating solution for 100 minutes at 100 rpm using a rotary coating machine.
Dry for 2 minutes in oven at ℃. The thickness of the obtained photosensitive layer was 5 μm. Using a laminator, a polypropylene film (thickness: 12 μm) was neminated on the photosensitive layer to produce a photosensitive element.

Next, the following coating solution for a toner layer was prepared. (1) Preparation of Mother Solution A 20% by weight solution of polyvinyl butyral A (manufactured by Denki Kagaku Kogyo KK, Denka Butyral # 2000-L, number average polymerization degree: about 300, butyralization degree: 73% by weight) (solvent: n-propyl alcohol) 63 parts by weight Coloring material (cyan pigment, manufactured by Toyo Ink Co., Ltd., No. 700-Blue 10FG CY-Blue) 12 parts by weight Glass beads 100 parts by weight Dispersing aid (manufactured by ICI Corporation) Solsperse S-20000) 0.8 parts by weight Dispersing aid (manufactured by ICI Co., Ltd., Solsperse S-12000) 0.2 parts by weight Solvent: n-propyl alcohol 60 parts by weight A paint shaker (Toyo Seiki Co., Ltd.) stock)
For 2 hours to prepare a mother liquor.

(2) Preparation of Coating Solution 24 parts by weight of mother liquor Solvent: 100 parts by weight of n-propyl alcohol Surfactant (manufactured by Dainippon Ink Co., Ltd., trade name Megafax F-176PF) 0.36 parts by weight The components were mixed with stirring with a stirrer to prepare a coating solution for a toner layer.

On a surface of a support (b) of a polyethylene terephthalate (PET) film having a thickness of 75 μm, the above-mentioned coating solution was applied for 300 rpm by using a rotary coating machine (whiter).
pm for 1 minute and dried in a 100 ° C. oven for 2 minutes to form a cyan toner layer to form a toner element. The optical density of the obtained toner layer measured with a Macbeth densitometer using a green filter was 0.64.

Using the photosensitive element and toner element obtained by the above procedure, an image was formed by the following procedure, and the image was evaluated.

A test chart for printing plate printing (photomask) was attached to the cover film side of the photosensitive element by vacuum suction to bring the test chart into close contact therewith. Ultraviolet light from a 1 kW ultra-high pressure mercury lamp was applied through a photomask for 60 seconds from a distance of 100 cm. The cover film of the photosensitive element is peeled off, and the photosensitive layer of the photosensitive element is brought into close contact with the toner layer of the toner element.
℃, pressure 4.5kg / cm ² laminator set,
It passed at a speed of 450 mm / min. When the toner element is peeled off from the photosensitive element after returning to room temperature, a toner image corresponding to the exposed area on the photosensitive layer is formed on the support of the toner element, and the photosensitive layer is not exposed on the photosensitive layer of the photosensitive element. A toner image corresponding to the area was formed.

With respect to the image formed on the toner element, the resolution line width and the resolution at 200 halftone dots were measured by microscopic observation. Table 1 shows the results.

Example 2 Polyvinyl butyral A in a toner layer coating solution was converted to polyvinyl butyral B (Denka Butyral # 3000-1, manufactured by Denki Kagaku Kogyo KK, number average polymerization degree: about 630, butyralization degree: 75) % By weight) and the same amount was used to prepare a toner element in the same manner as in Example 1.

An image was formed in the same manner as in Example 1 using the toner element and the photosensitive element prepared in the same manner as in Example 1, and the image was evaluated. Table 1 shows the evaluation results.

Example 3 Polyvinyl butyral A in a toner layer coating solution was converted to polyvinyl butyral C (Denka Butyral # 3000-2, manufactured by Denki Kagaku Kogyo KK, number average polymerization degree: about 700, butyralization degree: 75) % By weight) and the same amount was used to prepare a toner element in the same manner as in Example 1.

Using the toner element and the photosensitive element prepared in the same manner as in Example 1, an image was formed in the same manner as in Example 1, and the image was evaluated. Table 1 shows the evaluation results.

[Comparative Example 1] Polyvinyl butyral A in a toner layer coating solution was converted to polyvinyl butyral D (Denka Butyral # 4000-1, manufactured by Denki Kagaku Kogyo KK, number average polymerization degree: about 920, butyralization degree 75) % By weight) and the same amount was used to prepare a toner element in the same manner as in Example 1.

An image was formed in the same manner as in Example 1 by using the toner element and the photosensitive element prepared in the same manner as in Example 1, and the image was evaluated. Table 1 shows the evaluation results.

[Comparative Example 2] Polyvinyl butyral A in the toner layer coating solution was converted to polyvinyl butyral E (Denka Butyral # 5000-A, manufactured by Denki Kagaku Kogyo KK, number average polymerization degree: about 2,000, butyralization degree: 80) % By weight) and the same amount was used to prepare a toner element in the same manner as in Example 1.

Using the toner element and the photosensitive element prepared in the same manner as in Example 1, an image was formed in the same manner as in Example 1, and the image was evaluated. Table 1 shows the evaluation results.

Comparative Example 3 Polyvinyl butyral A in the toner layer coating solution was converted to polyvinyl butyral F (Denka Butyral # 6000-C, manufactured by Denki Kagaku Kogyo KK, number average polymerization degree: about 2400, butyralization degree: 80) % By weight) and the same amount was used to prepare a toner element in the same manner as in Example 1.

Using the toner element and the photosensitive element prepared in the same manner as in Example 1, an image was formed in the same manner as in Example 1, and the image was evaluated. Table 1 shows the evaluation results.

[0117]

[Table 1]

Example 4 A coating solution for an intermediate layer having the following composition was prepared. Polymer Ethylene-ethyl acrylate copolymer 20 parts by weight (Mitsui Petrochemicals Co., Ltd., trade name Eveflexs A-709) Solvent (toluene) 100 parts by weight Polyethylene terephthalate (PE) having a thickness of 100 μm
T) Using a film as a support, the above coating solution was applied at 200 rpm for 1 minute using a spin coater, and dried in an oven at 100 ° C. for 2 minutes. The thickness of the obtained intermediate layer was 20 μm.

A coating solution for a photosensitive layer having the following composition was prepared. Here, photoinitiators B and C are chloroform 1 ml.
0.45 g was used.

Binder 9.0 parts by weight (Allyl methacrylate / methacrylic acid copolymer, copolymer composition ratio = 80/20 (molar ratio), molecular weight = 36,000) Dipentaerythritto hexaacrylate 1 0.2 parts by weight (photopolymerizable monomer, abbreviated as DPHA) Photoinitiator B (structural formula B) 0.045 parts by weight (solid content)

[0121]

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Photoinitiator C (Structural Formula C) 0.045 parts by weight (solid content)

[0123]

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Hydroquinone monomethyl ether 0.01 parts by weight (thermal polymerization inhibitor) 1-methoxy-2-propanol 21 parts by weight

The above-mentioned coating solution for a photosensitive layer was applied on the above-mentioned intermediate layer at 100 rpm for 1 minute by using a rotary coating machine, and dried in an oven at 100 ° C. for 2 minutes. The thickness of the obtained photosensitive layer was 5 μm. Using a laminator on this photosensitive layer, a polypropylene film (thickness 1
2 μm) to produce a photosensitive element.

Using the photosensitive element obtained by the above procedure and the toner element produced in the same manner as in Example 1,
An image was formed by the following procedure, and the image was evaluated.

First, a photosensitive element was attached on a rotating drum such that the laser incident surface became a cover film. Next, the rotating drum was rotated at a linear velocity of 3 m / sec, and scanning and exposure were performed with an argon ion laser (wavelength: 488 nm) under the conditions of a power of 1.5 mW on the sample surface and a beam diameter of 10 μm. At this time, the recording pattern has a line pitch of 20 μm.
Laser scanning was performed so as to be a straight line. After peeling off the cover film of the photosensitive element, a laminator set at 110 ° C. and a pressure of 4.5 kg / cm ² was applied for 450 m while the toner layer of the toner element and the photosensitive layer of the photosensitive element were in contact with each other.
It was passed at a speed of m / min. By peeling the toner element which had returned to room temperature from the photosensitive element, a toner image was formed on the photosensitive layer and the toner layer support.

The obtained images had good sensitivity, and all of the images had excellent resolving power and very few defects visually observed.

Example 5 Cyan having the following composition:
Magenta, yellow and black coating solutions were prepared for the respective toner layers.

<Cyan toner layer coating solution> (1) Preparation of mother liquor Polyvinyl butyral A (manufactured by Denki Kagaku Kogyo KK, Denka butyral # 2000-L, number average polymerization degree: about 300, butyralization degree 73 weight) %) Solution (solvent: n-propyl alcohol) 63 parts by weight Colorant (cyan pigment, manufactured by Toyo Ink Co., Ltd., No. 700-Blue 10FG CY-Blue) 12 parts by weight Glass beads 100 parts by weight Dispersion aid 0.8 parts by weight of an agent (Solsperse S-20000, manufactured by ICI) 0.2 parts by weight of a dispersion aid (Solsperse S-12000, manufactured by ICI) Solvent: 60 parts by weight of n-propyl alcohol The paint shaker (Toyo Seiki Co., Ltd.)
For 2 hours to prepare a mother liquor.

(2) Preparation of coating liquid Mother liquid 24 parts by weight Solvent: n-propyl alcohol 100 parts by weight Surfactant (manufactured by Dainippon Ink Co., Ltd., trade name: Megafac F-176PF) 0.36 parts by weight The components were mixed with stirring with a stirrer to prepare a coating solution for a toner layer.

<Magenta Toner Layer Coating Solution> (1) Preparation of Mother Solution 63 parts by weight of a 20% by weight solution of polyvinyl butyral A (Denka Butyral # 2000-L, manufactured by Denki Kagaku Kogyo KK) (solvent: methyl ethyl ketone) Coloring material (magenta pigment, manufactured by Toyo Ink Co., Ltd., Lionol Red LX-235) 12 parts by weight Glass beads 100 parts by weight Dispersing aid (manufactured by ICI Co., Ltd., Solsperse S-24000) 0.6 parts by weight Dispersing aid 0.2 part by weight of agent (manufactured by ICI Corporation, Solsperse S-22000) Solvent: 60 parts by weight of methyl ethyl ketone The above components were added to a paint shaker (Toyo Seiki Co., Ltd.)
For 2 hours to prepare a mother liquor.

(2) Preparation of coating liquid Mother liquid 24 parts by weight Solvent: methyl ethyl ketone 24 parts by weight Solvent: propylene glycol monomethyl ether acetate 98 parts by weight Surfactant (manufactured by Dainippon Ink Co., Ltd., trade name: Megafac F-176PF) 0.3 parts by weight The above components were mixed with stirring with a stirrer to prepare a coating solution for a toner layer.

<Yellow toner layer coating solution> (1) Preparation of mother liquor 63 parts by weight of a 20% by weight solution of polyvinyl butyral A (Denka Butyral # 2000-L, manufactured by Denki Kagaku Kogyo KK) (solvent: methyl ethyl ketone) Coloring material (yellow pigment, manufactured by Toyo Ink Co., Ltd., No. 1401-G-Lionol Yellow) 12 parts by weight Glass beads 100 parts by weight Dispersing aid (manufactured by ICI Corporation, Solsperse S-24000) 0.6 part by weight 0.2 parts by weight of dispersing aid (manufactured by ICI Co., Ltd., Solsperse S-22000) Solvent: methyl ethyl ketone 60 parts by weight A paint shaker (Toyo Seiki Co., Ltd.)
For 2 hours to prepare a mother liquor.

(2) Preparation of Coating Solution 31 parts by weight of mother liquor Solvent: 78 parts by weight of methyl ethyl ketone Solvent: 29 parts by weight of propylene glycol monomethyl ether acetate Surfactant (manufactured by Dainippon Ink Co., Ltd., trade name: Megafac F-176PF) 0.2 parts by weight The above components were mixed with a stirrer under stirring to prepare a coating solution for a toner layer.

<Coating Solution for Toner Layer for Black> (1) Preparation of Mother Solution A 20% by weight solution of polyvinyl butyral A (Denka Butyral # 2000-L, manufactured by Denki Kagaku Kogyo KK) (solvent: n-propyl alcohol) 63 parts by weight Color material (black pigment, manufactured by Mitsubishi Kasei Kogyo Co., Ltd., type MA-100) 12 parts by weight Glass beads 100 parts by weight Dispersing aid (Kusumoto Kasei Co., Ltd., Dispalon KS-860) 18 parts by weight Solvent : Methyl ethyl ketone 42 parts by weight A paint shaker (Toyo Seiki Co., Ltd.)
For 2 hours to prepare a mother liquor.

(2) Preparation of Coating Solution 10 parts by weight of mother liquor Solvent: 50 parts by weight of n-propyl alcohol Solvent: 30 parts by weight of surfactant Surfactant (manufactured by Dainippon Ink Co., Ltd., trade name: Megafac F-176PF) 0 .15 parts by weight The above components were mixed with a stirrer under stirring to prepare a coating solution for a toner layer.

Using a polyethylene terephthalate (PET) film having a thickness of 75 μm as a support, the above-mentioned toner layer coating liquid for each color is applied at 120 rpm for 1 minute using a rotary coater (whiter) with one color per support. And 10
The toner element was dried in an oven at 0 ° C. for 2 minutes to produce the toner elements of the above four colors. The thickness of the obtained toner layer was 0.2 μm for black, 0.4 μm for cyan, 0.4 μm for magenta,
And yellow 0.2 μm.

Next, a coating solution for an image receiving layer having the following composition was prepared. <Image receiving first layer> Polyvinyl chloride 9 parts by weight (manufactured by Nippon Zeon Co., Ltd., trade name: Zeon 25) Surfactant 0.1 weight part (manufactured by Dainippon Ink Co., Ltd., trade name: Megafac F-177P) 130 parts by weight of methyl ethyl ketone 35 parts by weight of toluene 20 parts by weight of cyclohexanone 20 parts by weight of dimethylformamide

<Image receiving second layer> Methyl methacrylate / ethyl acrylate / methacrylic acid copolymer (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianal BR-77) 17 parts by weight Alkyl acrylate / alkyl methacrylate copolymer 17 parts by weight (Manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianal BR-64) Pentaerythritol tetraacrylate 22 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-TMMT) Surfactant 0.4 parts by weight (Dainippon Ink) (Trade name, MegaFac F-177P) Methyl ethyl ketone 100 parts by weight Hydroquinone monomethyl ether 0.05 part by weight 2,2 dimethoxy-2-phenylacetophenone (photopolymerization initiator) 1.5 parts by weight

Using a 100 μm thick polyethylene terephthalate (PET) film as a support, the above-mentioned coating solution for the first image receiving layer was applied using a spin coater (Wheyer) and dried in an oven at 100 ° C. for 2 minutes. The thickness of the obtained first layer was 1 μm. On the first layer, a coating was applied in the same manner using the above-mentioned coating solution for an image receiving second layer, and an image receiving second layer having a dry film thickness of 26 μm was laminated to produce an image receiving element.

The photosensitive element produced in the same manner as in Example 1, the four-color toner element produced as described above,
And a multicolor image was formed on the image receiving element by the following procedure.

First, a black toner image was formed on the black toner element from the photosensitive element and the black toner element in the same manner as in Example 1. Obtained
The toner layer of the black toner element on which the image is formed,
Superimposed on the image receiving layer of the image receiving element in a face-to-face relationship;
Lamination was performed at 25 ° C., a pressure of 4.5 kg / cm ² , and a speed of 450 mm / min. After cooling to room temperature, the image receiving element and the toner element were separated from each other. As a result, a black toner image (toner layer) on the toner layer support was transferred onto the image receiving layer.

Using a new photosensitive element and a cyan toner element, a cyan toner image was formed on the cyan toner element in the same manner as described above. The obtained toner layer of the toner element on which the cyan image is formed is superimposed on the image receiving layer on which the black toner image is formed in a face-to-face relationship so that the recording lines are perpendicular to each other. When combined, laminated and separated under the same conditions, on the image receiving layer,
The orthogonal black and cyan image lines were well transferred.

Subsequently, the same operation is performed for the magenta toner element and the yellow toner element, so that a multicolor image composed of black, cyan, magenta and yellow toner layers is formed on the image receiving layer of the image receiving element. Formed.

An image receiving element having an image receiving layer on which the above-described four color toner layers are transferred and on which a multicolor image is formed is overlapped so that the art paper used for printing and the image receiving layer have a face-to-face relationship. The laminate was laminated under the conditions of 125 ° C., a pressure of 4.5 kg / cm ² , and a speed of 450 mm / min. From the image receiving element side of this laminate, a 1 kW ultra-high pressure mercury lamp, 100 c
The entire surface was irradiated with light at a distance of m, and then the image receiving element was peeled off. As a result, it was confirmed that the toner image layers of the four colors were transferred onto the art paper with good adhesion. The obtained image was excellent in resolving power, there was no change in hue, and there were very few defects visually observed.

[0147]

According to the image forming method of the present invention, a color image can be obtained by a dry development method. In particular, the image forming method of the present invention has a remarkable effect that a color proof can be directly obtained by laser light digitally modulated with an image signal.

According to the image forming method of the present invention, an image using a pigment as a coloring material can be formed on a printing paper, so that a proof having high print similarity can be obtained. The resulting image does not involve discoloration due to the sensitizing dye. In addition, since color matching is performed on a plastic support having excellent dimensional stability, there is a remarkable effect that the process stability is high and the mechanical strength of the obtained image is also excellent.

[Brief description of the drawings]

FIG. 1 is used in the image forming method of the first invention.
FIG. 2 is a cross-sectional view schematically illustrating a cross section of an example of a photosensitive element.

FIG. 2 is a cross-sectional view schematically showing a state of the photosensitive layer when the photosensitive layer of the photosensitive element is imagewise exposed to actinic rays in the image forming method of the first invention.

FIG. 3 is a cross-sectional view schematically showing a state in which an example of a photosensitive element having a latent image formed on a photosensitive layer in step (B) of the first invention is in contact with an example of a toner element.

FIG. 4 is a cross-sectional view schematically showing a state in which a toner element is separated from a photosensitive element in a step (C) of the first invention.

FIG. 5 is a cross-sectional view schematically showing a state in which an example of a toner element on which an image obtained in step (C) of the second invention has been formed is brought into contact with an example of an image receiving element.

FIG. 6 is a cross-sectional view schematically showing a state in which a support (b) 22 is separated from an image receiving element 31 in a step (D) of the second invention.

FIG. 7 shows an image of hue AA and hue BB according to the third invention.
FIG. 3 is a cross-sectional view schematically showing a state in which the image of FIG. 1 is formed on an image receiving layer of an image receiving element.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Photosensitive element 12 Support (a) 13 Photosensitive layer 21 Toner element 22 Support (b) 23 Toner layer 31 Image receiving element 32 Support (c) 33 Image receiving layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/34 G03F 7/34 (72) Inventor Fumiaki Shinozaki 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Fujisha Shin Film Co., Ltd. (56 References JP-A-63-206749 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/004, 7/033, 7/105, 7/28, 7/34

Claims (3)

(57) [Claims] 1. A support (a) comprising: (A) a photosensitive layer which shows tackiness when exposed to actinic light when not exposed and shows non-adhesion after exposure.
Forming a latent image by imagewise exposing the photosensitive layer of the photosensitive element having active light rays to actinic light; (B) supporting a toner layer containing a colorant and a binder on the photosensitive layer on which the latent image is formed; Body (b)
Contacting the toner layer of the toner element thereon in a face-to-face relationship; and (C) separating the toner element from the photosensitive element to expose a portion of the toner layer corresponding to the unexposed portion of the photosensitive layer. Image forming method comprising the steps of: transferring a toner layer on the support (b), transferring the toner layer to the exposed portion of the photosensitive layer, and leaving an image on the support (b). Wherein the binder is from 200 to 800.
An image forming method comprising a thermoplastic resin containing polyvinyl butyral having a number average degree of polymerization within the range described above and a butyralization degree within the range of 50 to 85% by weight as a main component. 2. A support (a) comprising: (A) a photosensitive layer exhibiting tackiness to actinic rays when not exposed and exhibiting non-stickiness after exposure.
Forming a latent image by imagewise exposing the photosensitive layer of the photosensitive element having active light rays to actinic light; (B) supporting a toner layer containing a colorant and a binder on the photosensitive layer on which the latent image is formed; Body (b)
(C) separating the toner element from the photosensitive element and bringing a portion of the toner layer corresponding to a non-exposed portion of the photosensitive layer onto the photosensitive layer; (D) forming an image composed of a toner layer on the support (b) by leaving the portion of the toner layer corresponding to the exposed portion of the photosensitive layer on the support (b), and Is contacted in a face-to-face relationship with an image receiving layer of an image receiving element having an adhesive image receiving layer on a support (c), and then the toner element is separated from the image receiving element. Transferring the toner layer on which the image has been formed to an image receiving element.
An image forming method comprising a thermoplastic resin containing polyvinyl butyral having a number average polymerization degree in the range of 0 to 800 and a butyralization degree in the range of 50 to 85% by weight as a main component. 3. A support (a) comprising a photosensitive layer which exhibits tackiness to actinic light when not exposed to light and exhibits tackiness after exposure to light.
Forming a latent image by imagewise exposing the photosensitive layer of the photosensitive element having active light rays to actinic light; (B) supporting a toner layer containing a colorant and a binder on the photosensitive layer on which the latent image is formed; Body (b)
Contacting the toner layer of the toner element thereon in a face-to-face relationship; and (C) separating the toner element from the photosensitive element to expose a portion of the toner layer corresponding to the unexposed portion of the photosensitive layer. Transferring the toner image onto the support (b) to form an image composed of the toner layer on the support (b) by leaving the portion of the toner layer corresponding to the exposed portion of the photosensitive layer on the support (b). For each of the two or more types of toner elements, (D) the toner layer on which the image is formed is surface-to-face with the image receiving layer of the image receiving element having the image receiving layer having an adhesive surface on the support (c). The step of separating the toner element from the image receiving element and transferring the toner layer on which the image has been formed to the image receiving element after contacting them in a surface relationship, for the two or more toner elements having different hues and one image receiving element; It is possible to form a multicolor image by repeating Wherein the binder comprises polyvinyl butyral having a number average degree of polymerization in the range of 200 to 800 and a degree of butyralization in the range of 50 to 85% by weight as a main component. An image forming method, which is a resin.