JP2003029428A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method which is capable of efficiently and rapidly forming images of high image quality having excellent resolution and dot reproducibility by simple process steps with a dry process. SOLUTION: This image forming method has a latent image forming process step of forming the latent images by subjecting a colored photosensitive layer 12 of a photosensitive material 14 having, successively from a base 11 side, the colored photosensitive layer 12 and an adjacent layer 13 adjacent to the colored photosensitive layer 12 on the base 11, to imagewise exposure, a laminating process step of bringing the photosensitive material 14 formed with the latent images and an image receiving material 17 into contact wit each other and laminating both materials by heating and/or pressurizing, an image forming process stage of forming the images 18 on the image receiving material 17 by peeling the photosensitive material 14 and the image receiving material 17 and transferring the colored photosensitive layer 12 of at least the exposed segments onto the image receiving material 17. The image forming method comprises forming the multicolor images by repeating, >=2 times, the latent image forming process step, laminating process step and image forming process stage described above by using the same image receiving material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method by dry development. Specifically, a color proof for print proofing, in particular, a method for directly obtaining a color proof from a digital signal by laser recording (Digital Dir).
ect Color Proof) and a multicolor image forming method useful for manufacturing a multicolor display.

[0002]

2. Description of the Related Art In the field of graphic arts, a printing plate is printed using a set of color separation films from a color original, and a color proof is created from the color separation film before the actual printing. Generally, an error check in the disassembling process, a necessity check for color correction, and the like are performed. As a material for this color proof, it is said that it is preferable to use a pigment as a coloring material together with the image formation on the actual printing paper because of its high similarity to a printed matter. Further, in recent years, a dry proof making method which does not use a developing solution is required together with a high resolving power which enables a high reproducibility of a halftone image and a high process stability.

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

On the other hand, in place of these printing methods, various proofreading methods by photographic methods have been developed as a more convenient and simple method. A color proofing method using a photopolymer (prepress proof) is one of the color proofing methods based on these photographic methods and is widely used.

In the case of a photopolymerization system, which is a typical system of photopolymers, many methods as described below have been put to practical use for the conventional process of exposing using an intermediate film by a photographic method as a mask. In order to obtain a high-quality color proof, it is generally necessary to reproduce a halftone dot image of 150 lines / inch or more, but in this method, resolution is basically high enough. Further, most of the conventional photopolymerization initiators are exposed to the near-ultraviolet region, but on the other hand, as shown in JP-A-54-155292, a spectral sensitizer which extends the photosensitive wavelength region to the visible region is used. Many have been developed to date. Therefore, it is relatively easy to realize high recording sensitivity for a laser having a visible light wavelength such as an argon ion laser or a helium cadmium laser.

Here, due to the recent spread of computerized systems in the pre-printing process (prepress field), the demand for shortening the process, and reducing the consumption of consumables such as films, it is not necessary to use intermediate materials such as lith films. There is an increasing demand for materials and recording systems that produce color proofs directly from digital image signals. Therefore, in order to record a high-quality proof from a digital signal, it is preferable to use a laser beam that can be modulated by the digital signal and that can narrow down the recording light as a recording head. Therefore, the recording material is required to have high resolution 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 a quality for practical use has not been developed yet.

The above-mentioned photopolymerization system has a high potential for digital image recording in terms of resolution and laser recording sensitivity, but it has not yet been put to practical use. The following is an overview of the prior art of photographic multicolor image recording using a photopolymerizable material, and its problems are shown.

As a conventional proofing method for color printing by a photographic method, there are an overlay method and a surprint method. The overlay method is a method of calibrating by preparing multiple color proofing sheets with separated images of each color on a transparent support and stacking these sheets (the obtained one is called a color test sheet). Is.

This overlay method is simple and inexpensive,
Each time, it has the advantage that it can be used for continuous inspection by stacking only 2 or 3 colors, but the stacked synthetic resin sheets make the color test sheet slightly darker and the incident light from several sheets The impression given from the color test sheet is reflected and gives a gloss,
It has a very different drawback compared to the printed matter by the printing machine.

On the other hand, the surprint method is to superpose colored images of several colors on a single support, for which various colored layers are provided on a sheet of opaque base or the corresponding toner. Are sequentially provided on the 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 the coloring material. It is 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. By forming a colored image on the release layer,
Then, a method of transferring this colored image together with a release layer to an arbitrary support (permanent support) by using an adhesive is already known (Japanese Patent Publication No. 46-15326 and Japanese Patent Publication No. 49).
-441 publication). This method has the advantage that it can be used for various operations such as overlay proofing and surprinting as a color proof, but in order to transfer each color sequentially on a paper support with poor dimensional stability, It is difficult to maintain the registration accuracy of each color, and the mechanical strength of the finished image is weak.

As a method for improving the above-mentioned drawbacks, a method of temporarily transferring an image onto a temporary image-receiving sheet (image-receiving element) before transferring the image onto a permanent support is applied to the applicant of the present invention. 59-97140.
That is, in this method, a temporary image receiving element having an image receiving layer made of a photopolymerizable material provided on a support is prepared, and before the image of each color is transferred onto a permanent support, the temporary image receiving element is temporarily provided. Transfer the image of each color onto. Then, the step of retransferring onto the permanent support and further exposing the entire surface to cure the transferred photopolymerizable image-receiving layer is included. According to this method, alignment and transfer of each color image can be performed on a support such as polyethylene terephthalate, which has high dimensional stability, so that both alignment accuracy and quality stability are improved, and hardness is improved. Since the final image is protected by the large photo-curable layer, it also has an advantage that the mechanical strength of the image is excellent.
However, this method has an essential problem of a wet development method in principle.

Many multicolor image forming methods have been proposed in the past, which have solved the drawbacks of the wet development method, and some of them have been widely put into practical use. As an example, U.S. Pat. No. 3,063
No. 0,024, No. 3,582,327, No. 3,6
No. 20,726 and the like are known, and in these methods, an adhesive photopolymerization comprising a support layer and a photopolymerizable layer containing at least one addition-polymerizable monomer and a photopolymerization initiator. The potential reproduction material is cured by imagewise exposure and its loss of tack is utilized to make it visible by applying a suitable powdered toner material to the latent image formed. 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 developing method that does not require a developing solution and is also widely used for proof printing using a color separation film because of its simplicity. However, since the powdery toner is handled, the area around the work is easily soiled, and the way of applying / removing the toner easily varies 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 shown in, for example, JP-A-63-41847 and JP-A-2-14985. Has been done. In these methods, similarly to the above method, the tackiness in the unexposed state,
The photosensitive layer which loses its tackiness upon exposure / curing comprises a photopolymerizable monomer and a photoinitiator, and the photosensitive layer is used together with a support in the form of being 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-shaped toner provided on another support, and the toner is transferred by being heated and / or pressurized, It is developed. Of the two publications mentioned above, the former is characterized by mixing polymers which are incompatible with each other as a binder of the toner layer, and the latter is also selected the thermal and mechanical properties of the binder polymer of the toner layer. To improve the obtained image quality. These two methods all improve the above-mentioned drawbacks of the method using the powder toner, are excellent in the approximation of the printed matter (pigment image formation on the actual printing paper), can be dry-developed, and are stable in quality. Therefore, it can be said that the method is remarkably preferable as compared with the conventional method.

However, the methods using these film-formed toners still have problems to be solved. First, since the alignment of the image exposure of the photosensitive layer is repeated on the paper support having poor dimensional stability, misalignment of each hue image is likely to occur. Further, since the final image has low mechanical strength, if it is desired to impart scratch resistance, adhesion resistance and the like, it is necessary to add a complicated process such as laminating a protective layer on the final image. Furthermore, there are problems that the resolution and halftone dot reproducibility of the final image are insufficient, the film strength of the toner film is small, and the toner film is easily damaged during handling.

In order to solve the above-mentioned problems, the inventors of the present invention have previously disclosed, as an image forming method for directly forming a high-quality color proof having a high degree of approximation to a printed matter by a laser beam modulated with a digital image signal. 5-224427
The methods described in Japanese Patent Laid-Open No. 5-224428 and Japanese Patent Laid-Open No. 5-224428 are proposed. In these methods, a latent image is formed by imagewise exposing a photosensitive element that exhibits tackiness when not exposed and that exhibits non-adhesion after exposure, and the toner layers of the toner element are brought into contact in a face-to-face relationship and laminated. The toner element is separated from the photosensitive element to form an image, and the negative image of the toner layer remaining on the toner element is transferred to the image receiving element to form an image.

According to this method, even if a photopolymerization initiator having sensitivity in the visible region is used, there is an advantage that a high quality image can be obtained without worrying about coloring due to the initiator or the spectral sensitizing dye. It is suitable for the formation of DDCP, which requires high sensitivity. However, there have been problems such as the complicated image forming process and the increase in the number of supports to be scrapped. Further, since the transfer step is included between the exposure-peeling and developing step, there is a problem that dust and the like are mixed during the transfer in a dusty environment to cause minute image defects.

The dry peeling and developing method, which is the simplest method of the image forming process, is Chromacheck (Cromache) which is an overlay peeling system from DuPont.
ck) are commercially available, and this system and related systems are disclosed in U.S. Pat. Nos. 3,754,920, 4,282,308, 4,247,619, and 4,489. 153 and 4,316,951
No. In these methods, each color sheet is image-wise exposed and stripped to produce cyan, magenta, yellow, and black images on separate substrates, then the overlay proofs are simply overlaid by overlaying each color image. Is obtained. The photosensitive element comprises in turn a peelable cover sheet, a photoadhesive layer, a non-photosensitive adhesive adjoining layer and a substrate. The photoadhesive layer may be colored, in which case the image is immediately developed by image-wise irradiation and peeling. The adhesive adjacent layer generally comprises a soft, elastic resinous material. This method has the advantages that the assembly method is simple and can be performed quickly. However, as outlined above for the drawbacks of the overlay method,
These methods have a problem that a high-quality proof having high similarity to printed matter cannot be produced because a transparent plastic substrate is interposed.

Japanese Patent Laid-Open No. 6-214 discloses a negative-acting image forming system which is a dry peeling developing system and which can provide a surprint type proof with a relatively simple process.
No. 381 can be cited. Here, a negative image forming system using a color sheet having a photosensitive layer, a hydrophilic barrier layer and an adhesive layer on a cover sheet which is not easily adhesive is disclosed.

However, when the steps of transfer-exposure-peel development are repeated a plurality of times using the above materials to form a multicolor image, none of the steps can be performed in parallel, and the steps are In spite of its simplicity, there has been a problem that image formation takes much longer than expected.

[0021]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the problems in the prior art. That is, an object of the present invention is to provide an image forming method capable of forming a high-quality image having excellent resolution and halftone dot reproducibility by a simple process efficiently and in a short time in a dry method, The object is to achieve the object.

[0022]

Means for Solving the Problems <1> An addition polymerizable compound having an ethylenically unsaturated double bond (hereinafter also referred to as a polymerizable compound), a photopolymerization initiator and a colorant are contained on a support. And a latent image forming step of forming a latent image by imagewise exposing the colored photosensitive layer of a photosensitive material having a colored photosensitive layer and an adjacent layer adjacent to the colored photosensitive layer from the support side. A laminating step in which a light-sensitive material on which an image is formed and an image-receiving material are brought into contact with each other and heated and / or pressed to bond them, and the light-sensitive material and the image-receiving material are peeled off, and at least the colored light-sensitive layer at the exposed portion is subjected to the image-receiving. And an image forming step of forming an image on the image receiving material by transferring the latent image forming step, the laminating step and the image forming step twice using the same image receiving material. Repeat the above, multicolor image An image forming method characterized by forming an image.

<2> The <N> latent image forming process, which is the second or subsequent latent image forming process, is started at least before the (N-1) th image forming process is completed. This is an image forming method. <3> The image forming method according to <1> or <2>, wherein in the latent image forming step, the exposure is performed with a laser beam having a wavelength shorter than 450 nm.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION [Image Forming Method] The image forming method of the present invention will be described below. The image forming method of the present invention comprises a latent image forming step of imagewise exposing a colored photosensitive layer of a photosensitive material to form a latent image, and a step of heating the photosensitive material on which the latent image is formed and the image receiving material in contact with each other. And / or a laminating step of adhering under pressure, and an image forming step of separating the photosensitive material and the image receiving material, transferring at least the colored photosensitive layer of the exposed portion to the image receiving material, and forming an image on the image receiving material. That is, the latent image forming step, the laminating step, and the image forming step are repeated twice or more using the same image receiving material to form a multicolor image.

An example of the image forming method of the present invention will be described below with reference to the drawings. FIG. 1 is a process explanatory diagram of the image forming method of the present invention. FIG. 2 is an explanatory diagram of a multicolor image formed by the image forming method of the present invention.

(Latent Image Forming Step) As shown in FIG. 1A, in the latent image forming step, the adjacent layer 13 of the photosensitive material 14 having the colored photosensitive layer 12 and the adjacent layer 13 on the support 11 in this order. From the side, the colored photosensitive layer 12 is imagewise exposed.
In the exposed portion, the colored photosensitive layer 12 adheres to the adjacent layer 13 due to the action associated with the polymerization (crosslinking) reaction of the polymerizable compound in the colored photosensitive layer 12 to form a latent image. Although the exposure is performed from the adjacent layer 13 side in FIG.
You may expose from the side. However, exposure from the side of the adjacent layer 13 is preferable from the viewpoint of photosensitivity.

At the time of the exposure, ultraviolet rays such as a mercury lamp and a xenon lamp, laser light and the like can be used. When ultraviolet rays are used, the entire surface is irradiated through an image mask, and when laser light is used, the laser light modulated by the image signal is focused on the colored photosensitive layer to have an appropriate beam diameter and scanned to obtain an image. Can be exposed in the same manner. It is preferable to use a laser beam because imagewise exposure can be performed directly using digital data from an image processing system.

As the laser beam, a gas laser such as an argon ion laser, a helium neon laser, a helium cadmium laser, a solid-state laser such as a YAG laser, a semiconductor laser, etc., 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 into a half wavelength through a second harmonic element. The laser is appropriately selected from these lasers according to the photosensitive wavelength of the colored photosensitive layer, the sensitivity, and the required recording speed.

The light in the exposure in the latent image forming step preferably has a wavelength shorter than 450 nm and has a wavelength of 450 nm.
Preferable examples of the available laser light source having a shorter oscillation wavelength include the following. As a gas laser, Ar ion laser (364 nm, 351 nm,
10 mW to 1 W), Kr ion laser (356 nm,
351 nm, 10 mW to 1 W), He-Cd laser (441 nm, 325 nm, 1 mW to 100 mW), and Nd: YAG (YVO4) and SHG as solid-state lasers.
Crystal × 2 times combination (355 nm, 5 mW to 1
W), a combination of Cr: LiSAF and SHG crystals (4
30 nm, 10 mW) etc. as a semiconductor laser system,
KNbO3 ring resonator (430 nm, 30 mW), combination of waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm-450 nm, 5 mW-10
0 mW), Waveguide type wavelength conversion element and AlGaInP, Al
Combination of GaAs semiconductors (300nm-350n
m, 5 mW to 100 mW), AlGaInN (350n
m to 450 nm, 5 mW to 30 mW) and the like, as other pulse lasers, N ₂ laser (337 nm, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10).
~ 250 mJ) and the like. Among these, Al
A GaInN semiconductor laser (commercially available InGaN semiconductor laser 400 to 410 nm, 5 to 30 mW) is particularly preferable in terms of wavelength characteristics and cost.

The laser light is modulated by an image signal, for example, in the case of an Ar ion laser, the 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. Etc. are performed by a known method. Further, focusing of the modulated laser light on the colored photosensitive layer and scanning are also performed by a known method. In order to scan a laser beam, generally, a method of rotating a photosensitive material on a rotating drum at a high speed and moving a laser beam (sub-scanning) in synchronization with a direction perpendicular to the scanning direction (drum) Scanning method),
There is a method of moving (sub-scanning) the photosensitive element in the orthogonal direction while scanning the photosensitive element on the flat stage with a laser beam at a high speed (planar scanning method). In the present invention, any of these methods or their modified methods can be used.

(Laminating Step) As shown in FIG. 1B, in the laminating step, an image receiving layer 16 having an image receiving layer 16 on the surface of the adjacent layer 13 of the photosensitive material 14 on which a latent image is formed and a support 15 is formed. The surface of the image receiving layer 16 of the material 17 is superposed on and brought into contact with each other, and both are bonded by heating and / or pressing. The heating and pressing method is not particularly limited, but lamination with a heat roller is particularly preferable. in this case,
The temperature of the heat roller is preferably room temperature to 180 ° C., 70 ° C.
-150 degreeC is more preferable. The pressure of the heat roller is 0.
98 to 98 N (0.1 to 10 kgf / cm ² ) is preferable, and 9.8 to 49 N (1 to 5 kgf / cm ² ) is more preferable. The speed of the heat roller is 100 to 5000 mm /
min is preferable, and 300 to 2000 mm / min is more preferable. The conditions for these laminations are appropriately selected depending on the characteristics of the material used, such as thermal adhesion and the deformation strength of the support.

(Image Forming Step) As shown in FIGS. 1C and 1D, in the image forming step, the photosensitive material 14 and the image receiving material 17 are peeled off, and the adjacent layer 13 and the colored photosensitive layer in the exposed portion are peeled off. 12 is transferred to the image receiving material 17, and the image receiving material 17
An image 18 having the hue of the first color is formed on the top.

In this step, since the colored photosensitive layer 12 is transferred to the image receiving material 17 through the adjacent layer 13, it is possible to prevent dust and the like from entering the interface of the colored photosensitive layer 12 and suppress the occurrence of image defects. be able to. That is, if the adjacent layer 13 is not provided and dust or the like is present on the image receiving material 17, the colored photosensitive layer 12 of a necessary portion (exposed portion) is present.
However, there is a risk that image transfer will not be performed stably, resulting in image defects, but this can be suppressed. The peeling of the light-sensitive material and the image-receiving material is preferably carried out by deforming and peeling the support of the light-sensitive material so as to be folded back 180 °. Although the peeling speed is not particularly limited, it is preferably 100 to 100000 mm / min. Further, it is preferable that the peeling is performed by a machine so that the peeling speed and the peeling angle are not significantly changed.
Further, it is more preferable to provide some kind of adhesion means so that the image receiving material does not float up during peeling development. Examples of the adhesion means include a method in which the back surface of the image receiving material is vacuum-adhered and fixed by suction, and a method in which the back surface of the image receiving material is fixed with an adhesive having an adhesive property in a removable range.

In the image forming method of the present invention, for the images of the second and subsequent hues, the latent image forming step, the laminating step and the image forming step are repeated using the same image receiving material, and as shown in FIG. A multicolor image is formed on the image receiving material 17. Reference numeral 19 indicates an adjacent layer of the second color photosensitive material, and reference numeral 20 indicates an image of the second color hue. In the image formation of the hues of the second and subsequent colors, the N-th (N
Is preferably an integer of 2 or more) is started at least before the end of the (N-1) th image forming step. That is, for example, when forming the image of the second color, before the image forming step of the first color is completed, for example,
It is preferable to start the latent image forming step for the second color immediately after the latent image forming step for the first color is completed. By forming a multicolor image in this way, the time required for image formation can be shortened, and a high quality (high resolution and halftone dot reproducibility) multicolor image can be formed efficiently. .

Next, materials used in the image forming method of the present invention will be described. [Photosensitive Material] The photosensitive material used in the image forming method of the present invention has a colored photosensitive layer on a support and an adjacent layer adjacent to the colored photosensitive layer. In addition to these layers, an adhesive layer is provided. And other layers such as an undercoat layer may be included. Examples of the undercoat layer include layers described in JP-A-8-305004, which are provided between the support and the colored photosensitive layer and which contain a polymer having a phenol group.

<Colored Photosensitive Layer> The colored photosensitive layer contains an addition polymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator and a colorant. Further, if necessary, other components such as an organic polymer binder may be contained.

-Addition-Polymerizable Compound Having Ethylenically Unsaturated Double Bond- Examples of the addition-polymerizable compound having an ethylenically unsaturated double bond include polyfunctional vinyl and vinylidene compounds. Preferred polyfunctional vinyl or vinylidene compounds include, for example, unsaturated esters of polyols,
In particular, esters of acrylic acid or methacrylic acid, such as ethylene glycol diacrylate, glycerine 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, dipentaerythritol-polyacrylate, 1,3-propanediol-diacrylate, 1,5-pentanediol-dimethacrylate, Bis acrylates and bis polyethylene glycol having a molecular weight of from 00 to 400 - methacrylate and similar compounds, unsaturated amides,
Particular mention is made of unsaturated amides of acrylic acid and methacrylic acid having an α, ω-diamine whose alkylene chain may be opened by carbon atoms and ethylenebis-methacrylamide. Furthermore, for example, polyester acrylates obtained by condensation of esters of polyhydric alcohols and polyhydric organic acids with acrylic acid or methacrylic acid may be used, but are not limited thereto.

—Photopolymerization Initiator— As the photopolymerization initiator, a known photopolymerization initiator system can be used. For example, trihalomethyls such as trichloromethyltriazine and trichloromethyloxadiazole, benzophenone, Michler's ketone [4,4′-
Bis- (dimethylamino) benzophenone], 4,4 '
-Aromatic ketones such as bis- (dimeramino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenonetraquinone, and other aromatic ketones, benzoin,
Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzoin 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 US Pat. No. 3,
2,4,5-triacrylamidazole dimer similar to the dimer described in each specification of 476,185, British Patent 1,047,569 and US Pat. No. 3,784,557. Is used. The addition amount of the photopolymerization initiator is preferably 0.01 to 30% by mass of the mass of the polymerizable compound.

The photopolymerization initiator is 450
A system in which a dye (sensitizing dye) having a photosensitive wavelength in a shorter wavelength than nm and a photoradical generator are combined is more preferable. As the photo-radical generator, an organic boron compound and a titanocene compound are particularly preferable. The combined use of the dye having a photosensitive wavelength shorter than 450 nm and the photoradical generator significantly improves the sensitivity in the wavelength region corresponding to the absorption band of the dye. That is, it is considered that the dye having a photosensitive wavelength shorter than 450 nm functions as a sensitizing dye, absorbs exposure light, generates an excited state, and promotes initiation radical generation from a coexisting photoradical generator. (Such a process is called dye sensitization.) Of the above photo-radical generators, most of the titanocene compounds themselves have weak absorption in the wavelength range from ultraviolet to around 500 nm, but they are sensitive to wavelengths shorter than 450 nm. The photosensitivity is significantly improved by the dye having a wavelength. Therefore, even if the amount of the titanocene compound used is limited to a relatively small amount, the function of the dye can enhance the photosensitivity in a wavelength shorter than 450 nm, while the photosensitivity in a wavelength range of 450 nm or more is substantially no problem. It is possible to keep the sensitivity low. On the other hand, in the case of the organic boron compound, there is no absorption in the visible region, and even if the amount of the organic boron compound used is increased, the photosensitivity in the wavelength region of 450 nm or more does not pose a problem.

(A) Dye having a photosensitive wavelength shorter than 450 nm A dye (sensitizing dye) constituting the photopolymerization initiator and having a photosensitive wavelength shorter than 450 nm will be described below. As the dye, the following merocyanine dyes and carbonyl dyes are preferably used.

(A) -1 Merocyanine dye A dye having a photosensitive wavelength in the shorter wavelength than 450 nm (sensitizing dye).
Is preferably a merocyanine dye represented by the following general formula (1), and more preferably a sensitizing dye represented by the following general formula (2), general formula (3), or general formula (4).

[0042]

[Chemical 1]

In the general formula (1), A is an S atom or
Is NR¹Represents R¹Is a substituted or unsubstituted alkyl
Represents a group or a substituted or unsubstituted aryl group. Y
Is the basic nucleus of the dye with the adjacent A and carbon atoms.
Represents a non-metallic atomic group to be formed. X ¹And X²Are each independent
Represents a monovalent non-metallic atomic group, X¹, X²Tied to each other
They may combine to form the acidic nucleus of the dye.

[0044]

[Chemical 2]

In the general formulas (2), (3) and (4), A and Y have the same meanings as in the general formula (1). X ³ , X ⁴ and Z each independently represent an O atom, an S atom or NR ⁵ . R ⁵ represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group or arylamino group. R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group or an arylamino group. R ⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heteroaryl group.

The merocyanine dyes represented by the above formulas (1) to (4) are described in JP-A 2000-14776.
This is described in detail in paragraphs [0034] to [0070] of Japanese Patent Publication No.

The reason why the merocyanine dye is preferably used in the photosensitive element of the present invention is considered as follows. The absorption wavelength of a merocyanine dye is 350
The merocyanine dye having a specific structure in the present invention has a function of remarkably improving the photosensitivity of a photoradical generator such as a titanocene compound or an organic boron compound. Therefore, particularly when a titanocene compound is used, by limiting the amount used to a relatively small amount, the photosensitivity in the 500 nm region by the photoradical generator itself is substantially increased while the photosensitivity in the short wave is sufficiently enhanced. It is possible to reduce the sensitivity to a level that does not cause a problem. Further, the reason why the merocyanine dye having a specific structure in the present invention is particularly excellent in dye sensitizing ability cannot be described in detail because the mechanism of dye sensitization is unknown, but it can be considered as follows. That is, the merocyanine-based dye of the present invention is a π-electron system (the above general formulas (1) to (4) directly related to the absorption of the dye.
(AC = C-C = O portion) has a relatively rigid structure, and as a result, for example, JP-A-8-272.
As compared with the carbomerocyanine dyes described in JP-A-096 and JP-A-8-262715, the lifetime of the excited state caused by the light absorption of the dye may be longer and the efficiency of the dye-sensitized reaction may be higher. Conceivable. Further, the dye in the present invention has a lower electron donating property than other general dyes (the electrochemical oxidation / reduction potential is relatively positive. HOMO and LUMO based on the molecular orbital method). The orbital energy is negatively large.) It is considered to be a group of compounds, and it is considered that this is advantageous for improving the dye sensitization efficiency.

The preferred exemplary compounds (D1 to D52) of the sensitizing dyes represented by the above general formulas (1) to (4) are shown below, but the invention is not limited thereto.

[0049]

[Chemical 3]

[0050]

[Chemical 4]

[0051]

[Chemical 5]

[0052]

[Chemical 6]

[0053]

[Chemical 7]

[0054]

[Chemical 8]

[0055]

[Chemical 9]

(A) -2 Carbonyl dye As a dye (sensitizing dye) having a photosensitive wavelength in the shorter wavelength than 450 nm, a carbonyl dye represented by the following general formula (5) is also preferred.

[0057]

[Chemical 10]

In the above general formula (5), Z represents a non-metal atomic group forming a nitrogen-containing heterocycle with the adjacent N atom and carbon atom. X represents a monovalent nonmetallic atomic group. Z represents a non-metal atomic group forming a nitrogen-containing heterocycle, and examples of preferable nitrogen-containing heterocycle include, for example, F.I. M. Hamer, The Chemist
ry of Heterocyclic Compou
nds volume 18 "The Cyanine Dyes"
and Related Compounds "(19
64), John Willley & Sons (New)
And a nitrogen-containing heterocyclic group which constitutes the cyanine-based (Base) compound group described in York).

The carbonyl dye represented by the general formula (5) is described in detail in paragraphs [0011] to [0049] of JP-A 2000-98605. The general formula (5) in the present specification corresponds to the general formula (1) in JP-A-2000-98605, and Z in the general formula (5) in the present specification is in JP-A-2000- It corresponds to Y in the general formula (1) in Japanese Patent Publication No. 98605.

Further, the dye represented by the general formula (5) can be easily synthesized by a known synthesis method and its related synthesis method. A more specific synthesis method is, for example, Japanese Patent Publication No. 6-
It is described in detail in Japanese Patent No. 97339.

Hereinafter, preferred exemplary compounds (D53 to D10) of the carbonyl dye represented by the general formula (5) are shown.
5), but is not limited thereto.

[0062]

[Chemical 11]

[0063]

[Chemical 12]

[0064]

[Chemical 13]

[0065]

[Chemical 14]

[0066]

[Chemical 15]

[0067]

[Chemical 16]

[0068]

[Chemical 17]

(A) -3 Other sensitizing dyes Dyes having a photosensitive wavelength shorter than 450 nm (sensitizing dyes)
In addition to the merocyanine dyes and carbonyl dyes, among the “compounds represented by the general formulas (1) to (3)” described in Japanese Patent Application No. 2000-94431,
A compound having a photosensitive wavelength shorter than 450 nm is preferable. Below, the corresponding exemplary compounds (D106 to D
113) is shown.

[0070]

[Chemical 18]

[0071]

[Chemical 19]

Regarding the above compound, Japanese Patent Application No.
0-94431, paragraphs [0047] to [0]
112] and paragraphs [0281] to [0306].

(A) Photoradical generator Here, the photoradical generator used as the photopolymerization initiator will be described. The photo-radical generator used in the present invention is preferably an organic boron compound and a titanocene compound.

(A) -1 Organic Boron Compound As the photo-radical generator used in the photopolymerization initiator, an organic boron compound is preferable. The organic boron compound interacts with a dye (sensitizing dye) having a short-wave absorption shorter than 450 nm existing in the vicinity, interacts with the dye to generate a radical or the like with high efficiency, and exists in the vicinity. It has a function of initiating the polymerization of the addition-polymerizable compound.

As the organic boron compound, a compound represented by the following general formula (A), and "chemistry of functional dyes"
(1981, CMC Publishing Co., pp. 393-p. 41)
6) and "coloring material" (60 [4] 212-224 (198)
Examples include spectral sensitizing dye-based organic boron compounds having the cationic dye described in 7)) or the like as a cation moiety in the structure. Examples of the spectral sensitizing dye-based organic boron compound include JP-A-62-143044 and JP-A-1-1382.
No. 04, Tokuyohei 6-505287, Japanese Patent Laid-Open No. 4-261.
Examples thereof include compounds described in JP-A No. 406.

As the dye constituting the cation part of the spectral sensitizing dye-based organoboron compound, a cationic dye having a maximum absorption wavelength in a wavelength region of 300 nm or more, preferably 400 to 1100 nm is used. You can Among them, cationic methine dyes, polymethine dyes, triarylmethane dyes, indoline dyes, azine dyes, xanthene dyes, cyanine dyes, hemicyanine dyes, rhodamine dyes, azomethine dyes, oxazine dyes or acridine dyes are preferred, and cationic cyanines More preferred are dyes, hemicyanine dyes, rhodamine dyes or azomethine dyes.

Among the above organic boron compounds, the organic boron compounds represented by the following general formula (A) are more preferable in the present invention.

[0078]

[Chemical 20]

In the general formula (A), Ra ¹ , R
a ^2, and Ra ³ are each independently an aliphatic group, an aromatic group, a heterocyclic group, or an -SiRa ⁵ Ra ⁶ Ra ^7. Ra ⁴ represents an aliphatic group. Ra ^{1 to} Ra ³ and Ra ⁴
However, when it represents an aliphatic group, examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. Among these, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aralkyl group, or a substituted aralkyl group is preferable, and an alkyl group and a substituted alkyl group are particularly preferable. Further, the aliphatic group may be a cyclic aliphatic group or a chain aliphatic group. The chain aliphatic group may have a branch.

Examples of the alkyl group include linear, branched, and cyclic alkyl groups, and the number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20. The preferred range of the number of carbon atoms in the alkyl portion of the substituted alkyl group is the same as in the case of the alkyl group. The alkyl group may be an alkyl group having a substituent or an unsubstituted alkyl group.
As the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a neopentyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, Examples thereof include dodecyl group and octadecyl group.

Examples of the substituent of the substituted alkyl group include a carboxyl group, a sulfo group, a cyano group, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), a hydroxy group, and an alkoxycarbonyl group having 30 or less carbon atoms (eg, , Methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, acylaminosulfonyl group having 30 or less carbon atoms, Alkoxy group having 30 or less carbon atoms (eg, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), alkylthio group having 30 or less carbon atoms (eg,
Methylthio group, ethylthio group, methylthioethylthioethyl group, etc.), aryloxy group having 30 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro group, carbon number An alkyl group having 30 or less, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an acyloxy group having 30 or less carbon atoms (for example, an acetyloxy group, a propionyloxy group, etc.), an acyl group having 30 or less carbon atoms (for example, an acetyl group, Propionyl group, benzoyl group, etc., carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfur group) Famoyl group, morpholinosulfonyl , Or a piperidinosulfonyl group), aryl group having 30 or less carbon atoms (e.g., phenyl group, 4-
Chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino group (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, acylamino group, etc.), substituted ureido group, Examples thereof include a substituted phosphono group and a heterocyclic group. Here, the carboxyl group, sulfo group, hydroxy group, and phosphono group may be in a salt state. In that case, examples of the cation that forms a salt include Y + and the like described later.

Examples of the alkenyl group include linear, branched and cyclic alkenyl groups, and the number of carbon atoms of the alkenyl group is preferably 2 to 30, more preferably 2 to 20. Of the alkenyl part of the substituted alkenyl group,
The preferable range of the number of carbon atoms is the same as that of the alkenyl group. The alkenyl group may be an alkenyl group having a substituent or an unsubstituted alkenyl group. Examples of the substituent of the substituted alkenyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the alkynyl group include linear, branched, and cyclic alkynyl groups. The number of carbon atoms in the alkynyl group is preferably 2-30, more preferably 2-20. The preferable range of the number of carbon atoms of the alkynyl portion of the substituted alkynyl group is the same as that of the alkynyl group. The alkynyl group may be either an alkynyl group having a substituent or an unsubstituted alkynyl group. Examples of the substituent of the substituted alkynyl group include the same substituents as in the case of the substituted alkyl group.

Examples of the aralkyl group include linear, branched and cyclic aralkyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 35, more preferably 7 to 25. Of the aralkyl part of the substituted aralkyl group,
The preferable range of the number of carbon atoms is the same as that of the aralkyl group. Further, the aralkyl group may be either an aralkyl group having a substituent or an unsubstituted aralkyl group. As the substituent of the substituted aralkyl group,
The same substituents as in the case of the substituted alkyl group can be mentioned.

When Ra ^{1 to} Ra ³ represent an alkyl group of an aromatic group, examples of the aromatic group include an aryl group,
Substituted aryl groups are mentioned. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20. The preferred range of the number of carbon atoms in the aryl portion of the substituted aryl group is the same as that of the aryl group. Examples of the aryl group include a phenyl group, an α-naphthyl group, a β-naphthyl group, and the like. Examples of the substituent of the substituted aryl group include the same substituents as in the case of the substituted alkyl group.

When Ra ^{1 to} Ra ³ represent a heterocyclic group, examples of the heterocyclic group include a heterocyclic group having a substituent and an unsubstituted heterocyclic group. Examples of the substituent of the heterocyclic group having a substituent include the same substituents as those exemplified when Ra ^{1 to} Ra ³ represent an aryl group having a substituent. Among them, the heterocyclic group represented by Ra ^{1 to} Ra ³ is preferably a heterocyclic group containing a nitrogen atom, a sulfur atom, or an oxygen atom, such as a furan ring, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, or a pyridine ring. .

When Ra ^{1 to} Ra ³ represent -SiRa ⁵ Ra ⁶ Ra ⁷ , each of Ra ⁵ , Ra ⁶ and Ra ⁷ independently represents
It represents an aliphatic group or an aromatic group. Ra ⁵ , Ra ⁶ and Ra ⁷
Each independently represents an aliphatic group or an aromatic group. The aliphatic group and aromatic group have the same meanings as the aliphatic group represented by Ra ^{1 to} Ra ³ and Ra ⁴ and the aromatic group represented by Ra ^{1 to} Ra ³ , respectively, and the preferred examples are also the same.

In the general formula (A), Ra ¹ , R
Two or more of a ² , Ra ³ and Ra ⁴ may be linked directly or via a substituent to form a ring. When a ring is formed, the ring includes the following (C1) to (C
Any ring selected from the ring of 3) is preferable, and among them, the ring of (C2) is preferable.

[0089]

[Chemical 21]

In the ring (1), R _b represents the following divalent group.

[Chemical formula 22]

In the above general formula (A), Ra ¹ to Ra ³ are aryl groups and Ra is
^It is preferred that ⁴ is an alkyl group. In particular, a triarylalkyl type organic boron compound in which an aryl group is substituted with an electron-withdrawing group is preferable, and among them, the sum of Hammett (σ) values of the substituents (electron-withdrawing groups) on the three aryl groups. Is more preferably +0.36 to +2.58. The electron withdrawing group, a halogen atom,
A trifluoromethyl group is preferable, and a fluorine atom and a chlorine atom are particularly preferable.

The “electron-withdrawing group” means a substituent having a positive Hammett σ value. Here, the σ value is the “activity relationship of drugs-guideline for drug design and action mechanism research” in “Structure of Chemistry” Sensui 122, edited by the Structure-Activity Relationship Forum, pages 96-103, published by Nankodosha and Corbin.・ Hash (Corwin Hansch), Albert ・
Leo (Albert Leo), "Subtitutant Constants for Correlation Analysis in Chemistry and Biology"
(Substituent Constants fo
r Correlation Analysis in
Chemistry and Biology) 69
~ 161 pages, John Wiley and Sons (Jh
on Wiley and Sons, Corwin Hansch, A. Leo, RW Taft, Chemical Review (Che).
medical Reviews) Vol. 91, No. 165-19
It is described in page 5, etc. Further, regarding a substituent whose σ value is unknown, a chemical review (Chemical Review)
Reviews, 17: 125-136 (193)
It can be measured and determined by the method described in 5).

Examples of the aryl group substituted with an electron-withdrawing group include 3-fluorophenyl group, 4-fluorophenyl group, 2-fluorophenyl group, 3-chlorophenyl group,
4-chlorophenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-difluorophenyl group, 4-bromophenyl group, 3,4-
A difluorophenyl group, a 5-fluoro-2-methylphenyl group, a 5-fluoro-4-methylphenyl group, a 5-chloro-2-methylphenyl group, a 5-chloro-4-methylphenyl group and the like can be mentioned.

Specific examples of the anion moiety of the general formula (A) include, for example, tetramethylborate, tetraethylborate, tetrabutylborate, triisobutylmethylborate, di-n-butyl-di-t-butylborate and tetra. -N-butyl borate, tri-m-chlorophenyl-n-hexyl borate, triphenylmethyl borate, triphenylethyl borate, triphenylpropyl borate, triphenyl-n-butyl borate,
Trimesityl butyl borate, tritolyl isopropyl borate, triphenyl benzyl borate, m-fluoro-tetrabenzyl borate, triphenyl phenethyl borate, triphenyl-p-chlorobenzyl borate, triphenyl ethenyl butyl borate, di (α-naphthyl) -Dipropylborate, tri-n-butyl (dimethylphenylsilyl) borate, diphenyldihexylborate, tri-m-fluorophenylhexylborate, tri- (5-chloro-4-methylphenyl) hexylborate, tri-m-fluoro Phenylcyclohexyl borate, tri-m-fluorophenylbenzyl borate, tri- (5-fluoro-2-methylphenyl)
Hexyl borate and the like can be mentioned.

In the general formula (A), Y ⁺ represents a group capable of forming a cation. Among them, organic cationic compounds, transition metal coordination complex cations (such as the compounds described in Japanese Patent No. 2791143) or metal cations (for example, N
a ⁺ , K ⁺ , Li ⁺ , Ag ⁺ , Fe ²⁺ , Fe ³⁺ , Cu ⁺ , C
u ²⁺ , Zn ²⁺ , Al ³⁺ , 1 / 2Ca ^2+, etc.) are preferable.
Examples of the organic cationic compound include quaternary ammonium cation, quaternary pyridinium cation, quaternary quinolinium cation, phosphonium cation, iodonium cation, sulfonium cation, and dye cation.

As the quaternary ammonium cation,
Examples thereof include tetraalkylammonium cations (eg, tetramethylammonium cation, tetrabutylammonium cation), tetraarylammonium cations (eg, tetraphenylammonium cation), and the like. As the quaternary pyridinium cation,
N-alkylpyridinium cation (for example, N-methylpyridinium cation), N-arylpyridinium cation (for example, N-phenylpyridinium cation), N-alkoxypyridinium cation (for example,
4-phenyl-N-methoxy-pyridinium cation), N-benzoylpyridinium cation and the like. Examples of the quaternary quinolinium cation include N-alkylquinolinium cations (for example, N-methylquinolinium cation), N-arylquinolinium cations (for example, N-phenylquinolinium cation), and the like. To be Examples of the phosphonium cation include a tetraarylphosphonium cation (eg, tetraphenylphosphonium cation). Examples of the iodonium cation include a diaryliodonium cation (eg, diphenyliodonium cation). Examples of the sulfonium cation include a triarylsulfonium cation (eg, triphenylsulfonium cation).

Further, as specific examples of Y ⁺ , paragraphs [0020] to [0] of JP-A-9-188686 can be used.
[038] and the like.

In each of the above-exemplified cationic compounds (exemplary compounds), the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group,
An unsubstituted alkyl group such as an ethyl group, a propyl group, an isopropyl group, a butyl group, and a hexyl group, and the substituted alkyl group represented by Ra ^{1 to} Ra ⁴ are preferable. Especially, carbon number 1
Alkyl groups of 12 are preferred. In each of the above-exemplified cationic compounds, the aryl group is, for example, a phenyl group, a halogen atom (eg, chlorine atom) -substituted phenyl group, an alkyl (eg, methyl group).
A substituted phenyl group and an alkoxy (for example, methoxy group) substituted phenyl group are preferable.

Specific examples of the organic boron compound represented by the general formula (A) include US Pat. No. 3,567,453.
No. 4,343,891 and JP-A-62.
-143044, JP 62-150242 A, JP 9-188684 A, JP 9-188 A.
685, JP-A-9-188686, JP-A-9-188710, and JP-B-8-9643.
The compounds described in JP-A No. 11-269210 and the compounds (b-1 to 33) exemplified below are mentioned. However, the organoboron compound used in the present invention is not limited to these specific examples.

[0100]

[Chemical formula 23]

[0101]

[Chemical formula 24]

[0102]

[Chemical 25]

[0103]

[Chemical formula 26]

[0104]

[Chemical 27]

The organoboron compound represented by the general formula (A) is 0.01 to the content of the addition-polymerizable compound.
-20 mass% is preferred, and 0.1-10 mass% is more preferred. However, the preferred range varies depending on the type of the "addition-polymerizable compound" used in combination, and thus is not limited thereto.

(A) -2 Titanocene compound As the photoradical generator used in the photopolymerization initiator, a titanocene compound is also preferable. The titanocene compound may be any titanocene compound capable of generating an active radical when irradiated with light in the coexistence with the sensitizing dye. For example, JP-A-59-59
No. 152396, JP-A-61-151197, JP-A-63-41483, JP-A-63-41484, JP-A-2-249, JP-A-2-291, and JP-A-3-27.
393, JP-A-3-12403, JP-A-6-411.
Known compounds described in JP-A-70 can be appropriately selected and used.

More specifically, di-cyclopentadiethyl-Ti-di-chloride, di-cyclopentadiethyl-Ti-bis-phenyl, di-cyclopentadiethyl-Ti-bis-2,3,4,5. , 6-Pentafluorophenyl-1-yl (hereinafter also referred to as "T-1"), di-
Cyclopentadiethyl-Ti-bis-2,3,5,6-
Tetrafluorophenyl-1-yl, di-cyclopentadiethyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadiethyl-Ti-bis-2,6-difluorophenyl-1 -Yl, di-cyclopentadiethyl-Ti-bis-2,4-difluorophenyl-1-yl, di-methylcyclopentadiethyl-
Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadiethyl-T
i-bis-2,3,5,6-tetrafluorophenyl-
1-yl, di-methylcyclopentadiethyl-Ti-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadiethyl) -bis (2,6-difluoro-3)
-(Pyr-1-yl) phenyl) titanium (hereinafter "T
-2 ". ) Etc. can be mentioned.

The titanocene compound can be subjected to various chemical modifications in order to improve the characteristics of the colored photosensitive layer. For example, a bond with a sensitizing dye, an addition-polymerizable compound or other radical generating part, introduction of a hydrophilic site, improvement of compatibility, introduction of a substituent for suppressing crystal precipitation, introduction of a substituent for improving adhesion, polymerization Etc. can be used.

Regarding the method of using the titanocene compound,
It can be arbitrarily set depending on the performance design of the photosensitive material. For example, by using two or more titanocene compounds in combination, the compatibility with the colored photosensitive layer can be increased. A larger amount of the titanocene compound is usually advantageous in terms of photosensitivity, and is 0.5 to 80 relative to 100 parts by mass of the photosensitive layer component.
Sufficient photosensitivity can be obtained by using in the range of 1 part by mass, preferably 1 to 50 parts by mass. On the other hand, when used under a yellow light, which is the main purpose of the present invention, it is preferable that the amount of the titanocene compound used is small from the viewpoint of fog property due to light near 500 nm, Depending on the combination, the amount of titanocene compound used is 6
Parts by mass or less, further 1.9 parts by mass or less, further 1.4
Sufficient photosensitivity can be obtained even if the amount is reduced to less than or equal to parts by mass.

-Colorant-When the colorant is used as a proof for print proofing, it is more preferable that the colorant is a pigment like the one used for printing. Known pigments can be used, and examples thereof include carbon black, azo pigments, phthalocyanine pigments, quinacridone pigments, thioindigo pigments, anthraquinone pigments and isoindoline pigments. These may be used in combination of two or more, and a known dye may be added for adjusting the hue.

The colorant is 5 to 70% of the solid content of the colored photosensitive layer.
It is preferable that the content is 15% by mass to 50% by mass.
Is more preferable. If the amount is less than 5% by mass, it is necessary to increase the film thickness in order to obtain a desired optical density, which may cause a problem of lowering resolution. On the other hand, if the content is more than 70% by mass, the image formation itself may become difficult, or the scratch resistance of the colored photosensitive layer may be significantly lowered.

-Organic Polymer Binder- The colored photosensitive layer preferably contains an organic polymer binder. The organic polymer binder is one of the major factors not only determining the hardness of the colored photosensitive layer, but also its tackiness, affinity with adjacent layers, and affinity with the support. The organic polymer binder is not particularly limited, but when PVA is used for the adjacent layer, a homopolymer or copolymer of acrylic monomers such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, etc. Polymers, polystyrene, polyvinyl chloride, rubber-based polymers such as vinyl chloride-vinyl acetate copolymer, chlorinated rubber, butadiene-styrene copolymer, polyolefin-based polymers such as chlorinated polyethylene and chlorinated polypropylene are preferable. Are listed in. Among these, the copolymer of the acrylic monomer is preferable because it is easy to control the thermal properties such as the softening point in a wide range and the compatibility with the polymerizable compound is good.

The average molecular weight of the organic polymer binder is preferably 10,000 to 2,000,000. here,
The mixing ratio of the polymerizable compound and the organic polymer binder (polymerizable compound: organic polymer binder) varies depending on the combination of the polymerizable compound and the organic polymer binder used, but the aptitude ratio is 0.1. : 1.0 to 5.0: 1.0 (mass ratio) is preferable, and 0.5: 1.0 to 2.0: 1.0 (mass ratio) is more preferable. The colored photosensitive layer may contain known additives such as a thermal polymerization inhibitor, a plasticizer, and a surfactant as additives. As the layer thickness of the colored photosensitive layer,
It is preferably 0.1 to 3 μm, and 0.1 to 1.5
More preferably, it is μm.

<Adjacent Layer> The adjacent layer is a layer provided adjacent to the colored photosensitive layer, and has an ON / OFF function of the colored photosensitive layer and a function of preventing dust from entering the interface of the colored photosensitive layer as described above. . Further, it has a function of blocking the contact of the colored photosensitive layer with oxygen, and suppresses the decrease in the polymerization reactivity of the polymerizable compound in the colored photosensitive layer. For this adjacent layer, it is preferable to use various polymer materials that are colorless and transparent to both visible light and irradiation rays, materials that are incompatible with the colored photosensitive layer binder are preferable, and hydrophilic materials are more preferable.

Preferred materials used for the adjacent layer are proteins such as gelatin; polysaccharides and derivatives thereof such as starch, modified starch, xanthene, hydroxyalkyl cellulose, carboxyalkyl cellulose; and poly (vinyl alcohol) or hydroxyethyl acrylate. , A polymer such as acrylic acid and a copolymer such as a copolymer containing a large number of hydroxyl groups, carboxyl groups or other hydrophilic functional groups in the molecule. A particularly preferable material is poly (vinyl alcohol) (PVA), and one having a high degree of hydrolysis (for example, 90% or more) is more preferable. Adjacent layers can be crosslinked subsequent to coating and, if desired, can contain additives such as antihalation dyes (especially UV absorbing dyes). Further, as the material used for the adjacent layer,
The materials used for the photoadhesive layer described in JP-A-8-305004 can also be used. Various surfactants can be used in the adjacent layers. The addition amount is preferably 0.1 to 15 mass% of the total solid content of the adjacent layer. Further, the adjacent layer may contain various organic or inorganic matting agents, fillers and the like.

The thickness of the adjacent layer is 0.2 to 10 μm.
Is preferable, and 0.5-2.0 μm is more preferable. If the thickness is less than 0.2 μm, it may be difficult to exhibit various functions as an adjacent layer, which may be difficult.
If it exceeds μm, the problem of impairing the printed matter approximation may occur due to the influence of the optical dot gain.

<Adhesive Layer> The photosensitive material used in the image forming method of the present invention may have a structure in which a colored photosensitive layer, an adjacent layer and an adhesive layer are sequentially provided on a support. In particular, when polyvinyl alcohol is used as the adjacent layer, the provision of this adhesive layer makes the transfer to the image receiving material more stable. The adhesive layer preferably contains a material having thermoplasticity, and examples thereof include polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, acrylic acid ester copolymer, polymethacrylic acid ester, methacrylic acid ester copolymer, and polyacrylic acid. Acrylamide, acrylamide copolymer, polyvinyl acetate, vinyl acetate copolymer (for example,
Polyvinylpyrrolidone / vinyl acetate copolymer), polyvinyl chloride, vinyl chloride copolymer, polyvinylidene chloride,
Vinylidene chloride copolymer, polystyrene, styrene copolymer, ethylene copolymer (for example, ethylene / vinyl acetate copolymer, ethylene / vinyl chloride copolymer, ethylene / acrylic acid copolymer), polyvinyl acetal (for example, Polyvinyl butyral, polyvinyl formal),
Examples thereof include polyester resins, polyamide resins (eg nylon, copolymer nylon), various rubbers (eg synthetic rubber, chlorinated rubber), polyolefins (eg polyethylene, polypropylene), phenol resins, polyvinylpyrrolidone and the like. These materials may be used alone or in combination.

If desired, the adhesive layer may further contain various additives such as tackifying substances and plastic materials. Further, various fillers and the like may be included for the purpose of controlling tackiness. Examples of the filler include organic fillers such as polystyrene and PMMA, and inorganic fillers such as silica and alumina. Further, various surfactants can be used in the adhesive layer. The addition amount is preferably 0.1 to 15 mass% of the total solid content of the release layer.

The thickness of the adhesive layer is preferably 0.2 to 10 μm, more preferably 0.5 to 2.0 μm. If it is thinner than 0.2 μm, it may be difficult to obtain sufficient thermal adhesiveness, and if it is thicker than 10 μm, the problem of impairing the printed matter approximation may occur due to the influence of the optical dot gain.

<Support> The support is preferably substantially transparent, and is not particularly limited to a film or a plate, and may be made of any material. Since the support is substantially transparent, it is possible to suppress the scattering of light inside the support and to suppress the deterioration of resolution due to halation. Here, “substantially transparent” means that in the light-sensitive region and the visible light region,
Do not cause extreme light scattering (reflection), specifically,
It means that it is not white. Examples of the material of the support generally include polymer compounds such as polyethylene terephthalate, polycarbonate, polyethylene, polyvinyl chloride, polystyrene, and styrene-acrylonitrile copolymer, and biaxially stretched polyethylene terephthalate. It is particularly preferable in terms of mechanical strength and dimensional stability against heat.

The thinner the support is, the better the resolution is and the better it is, but it causes problems in handling such as wrinkles and the like. Therefore, a thickness of 3 to 100 μm is preferable, and 4.5 to 50 μm is more preferable. Further, the surface of the support, which comes into contact with the colored photosensitive layer, can be appropriately subjected to a release treatment. Examples of the release treatment agent include silicone-based and fluorine-based release agents, or “photo release (photo release) as described in US Pat. No. 5,028,511.
A polyester coated with a "release" layer can be used.

Further, it is preferable to introduce an antihalation layer containing an appropriate dye or pigment as an antihalation agent on the surface on which the layers of the support are laminated, or on the opposite surface, but a layer adjacent to the support Considering the possibility of adverse effects due to diffusion into the substrate, it is more preferable to introduce the support on the surface where the layers are not laminated. The dye or pigment used as the antihalation agent is not particularly limited as long as it is a compound having sufficient absorption at the absorption wavelength position of the initiator, and known materials can be used.

Each of the above layers can be formed by a known method. For example, a colored photosensitive layer coating liquid is applied to the surface of a support using a spin coater or the like, dried at 60 to 180 ° C. to form a colored photosensitive layer, and the adjacent layer coating liquid is formed on the colored photosensitive layer. Is coated using a spin coater or the like and dried at 60 to 180 ° C. to form an adjacent layer, whereby a photosensitive material can be prepared.

[Image Receiving Material] The image receiving material used in the image forming method of the present invention is not particularly limited as long as it can transfer the colored photosensitive layer of the photosensitive material, and the colored photosensitive material of the photosensitive material is provided on a support. The structure may have an image receiving layer capable of transferring the layer, or the support itself may serve as the image receiving layer.

(Support) The support is not particularly limited as long as it is a film or plate, and may be made of any material. Examples of the material of the support include polyethylene terephthalate, polycarbonate, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and polymer compounds such as styrene-acrylonitrile copolymer, and in particular, biaxially stretched polyethylene terephthalate. It is preferable in terms of dimensional stability against water and heat. Also, the thickness of the support is, in the case of a film,
10 to 400 μm is preferable, and 25 to 200 μm is more preferable. In the case of a plate, the thickness is preferably 100 to 3000 μm, more preferably 500 to 2000 μm. Further, depending on the application, glass, metal plate or the like can be used as the support.

The surface of the support may be provided with a laminated intermediate layer or may be subjected to a physical surface treatment in order to improve the adhesion to the image receiving layer. The intermediate layer is appropriately selected from a polymer material having a film-forming property in consideration of adhesion to both the support and the image receiving layer 22. The thickness is not particularly limited, but 0.01 to 2 μm is preferable. As the physical surface treatment means, glow discharge treatment, corona discharge treatment and the like on the surface of the support are preferable.

(Image-Receiving Layer) The image-receiving layer is preferably a polymer layer having a softening temperature lower than about 80 ° C. according to the Vicat method for receiving the colored photosensitive layer. Further, since it is transferred onto a printing paper as required, in order to obtain a proper release property, as a material for forming the image receiving layer, it is disclosed in JP-A-59 / 59.
It is preferably made of a photopolymerizable material as described in JP-A-97140.

Particularly preferred as the image-receiving layer are at least one photopolymerizable monomer or oligomer capable of forming a photopolymer by addition polymerization, at least one organic polymer binder (polymer binder), and at least one photopolymerization. It contains an initiator and an additive such as a thermal polymerization inhibitor which is added as necessary. Examples of the photopolymerizable monomer or oligomer include the same substances as those used in the colored photosensitive layer, and the organic polymer binder described above is used in the colored photosensitive layer. The same substances as those mentioned above can be mentioned.

The above-mentioned photopolymerization initiator must be a compound which has absorption and activity in the near-ultraviolet region and has no absorption in the visible region, or a small compound. Examples thereof include benzophenone, Michler's ketone [4,4′-bis- (dimethylamino) benzophenone], 4,4′-bis- (dimeramino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone. , Aromatic ketones such as phenone traquinone, and other aromatic ketones, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin ethers such as benzoin phenethyl ether, methylbenzoin, ethylbenzoin and other benzoins, And 2- (O-chlorophenyl) -4,5-
Examples thereof include photopolymerization initiators having an activity in the near ultraviolet region, such as diphenylimidazole dimer and 2- (O-chlorophenyl) -4,5- (m-methoxyphenyl) imidazole dimer.

Here, the mixing ratio of the photopolymerizable monomer and the organic polymer binder is different depending on the combination of the photopolymerizable monomer and the organic polymer binder to be used.
Generally, a photopolymerizable monomer: an organic polymer binder,
0.1: 1.0 to 2.0: 1.0 (mass ratio) is preferable. The addition amount of the photopolymerization initiator is preferably 0.01 to 20 mass% with respect to the photopolymerizable monomer.

The image-receiving layer can be formed by applying a coating solution for forming an image-receiving layer containing the above components onto a support and drying it according to a coating film forming method known per se. The thickness of the image receiving layer is preferably 1 to 50 μm, more preferably 5 to 20 μm.

The image receiving layer may have a two-layer structure, if desired. In particular, when the image on the image receiving layer is transferred to a permanent support such as printing paper in a later step, the upper layer of the two layers is transferred together with the image, and the lower layer (support side) is left on the image receiving element. Japanese Patent Laid-Open No. 61-189535, JP-A 2-24
It is described in detail in JP-A-4146, JP-A-2-244147 and JP-A-2-244148. The methods described in these publications are preferable from the viewpoint of closeness to printed matter and other points. Therefore, it is preferable that the image receiving layer has a two-layer structure.

[0133]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

A light-sensitive material was prepared as follows. First, a pigment dispersion A for a colored photosensitive layer (cyan pigment-containing dispersion) having the following composition was dispersed for 2 hours using a paint shaker (manufactured by Toyo Seiki Co., Ltd.).

[0135] ・ Benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio 73/27) Propylene glycol monomethyl ether acetate 27% solution                                                     ... 5.56 parts by mass Cyan pigment (C) (C.I.PB. 15: 4) ... 3.6 parts by mass Dispersion aid 1 (Solspers S-24000, manufactured by ICI Japan Co., Ltd.)                                                     ... 0.68 parts by mass Dispersion aid 2 (Solspers S-5000, manufactured by ICI Japan Co., Ltd.)                                                     ... 0.23 parts by mass ・ Solvent (Propylene glycol monomethyl ether acetate)                                                   ... 19.94 parts by mass ・ Glass beads: 17.50 parts by mass

With the above composition, the cyan pigment (C)
In the same manner except that the following pigments are used, the photosensitive layer pigment dispersion liquid B (magenta pigment-containing dispersion liquid), the photosensitive layer pigment dispersion liquid C (yellow pigment-containing dispersion liquid) and the photosensitive layer pigment dispersion liquid D ( A black pigment-containing dispersion) was prepared. The dispersion aid 2 was not used when preparing the pigment dispersion B for the photosensitive layer and the pigment dispersion C for the photosensitive layer.

[0137] ・ Magenta pigment (M) (C.I.PR. 57: 1) -Yellow pigment (Y) (CI.PY.180) ・ Black pigment (K) (CB-100)

The following compounds were mixed in each of the obtained pigment dispersions A to D for the photosensitive layer (15 parts by mass each), and a coating solution for the photosensitive layer was prepared using a stirrer.

[0139] ・ Methyl ethyl ketone ・ ・ ・ 134.69 parts by mass ・ Propylene glycol monomethyl ether acetate ... 44.90 parts by mass ・ Pentaerythritol tetraacrylate (75 wt% MEK solution)                                                     ... 3.36 parts by mass ・ Benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio 73/27) Propylene glycol monomethyl ether acetate 27% solution                                                     ... 1.78 parts by mass ・ Oxadiazole compound A: 0.126 parts by mass

[0140]

[Chemical 28]

Surfactant (manufactured by Dainippon Ink and Chemicals, Megafac F-176): 0.150 parts by mass

Four supports of polyethylene terephthalate (Lumirror manufactured by Toray Industries, Inc.) with a thickness of 6 μm were prepared, and the coating liquids A to D for the photosensitive layer were formed on the surfaces of the supports by using a spin coater (a whaler). It was coated and dried in an oven at 100 ° C. for 2 minutes to form cyan, magenta, yellow and black photosensitive layers. Each film thickness is 0.4μ
m, 0.4 μm, 0.8 μm, and 0.4 μm.

A coating liquid for an adjacent layer having the following composition was prepared using a stirrer. -Ion-exchanged water: 1520.00 parts by mass-Polyvinyl alcohol (Kuraray Co., Ltd., PVA-205): 100.00 parts by mass-Propylene glycol monomethyl ether: 380.00 parts by mass-Surfactant Agent (Asahi Glass Co., Ltd., Surflon S-131) ... 3.30 parts by mass

On each of the above colored photosensitive layers, a coating solution for an adjacent layer was applied using a spin coater (Whorer) to 100 ° C.
In an oven for 2 minutes. The thickness of the obtained adjacent layer was 2.0 μm.

An adhesive layer coating liquid having the following composition was prepared using a stirrer. N-PrOH ... 90.0 parts by mass PVP-VA E-735 (manufactured by ISP) ... 10.0 parts by mass Megafac F-176 (manufactured by Dainippon Ink and Chemicals) ... 0. 25 parts by mass

On each of the adjacent layers, the adhesive layer coating solution was applied using a wire bar # 6 and dried in an oven at 100 ° C. for 2 minutes. The thickness of the obtained adhesive layer is 0.5μ
It was m.

An image receiving material was prepared as follows. First, for the image receiving layer first layer and the image receiving layer second layer, the coating liquids for the image receiving layer having the following compositions were dissolved by using a stirrer, respectively.

[0148] Coating liquid for first layer of image receiving layer: ・ Polyvinyl chloride (Zeon 25 manufactured by Nippon Zeon Co., Ltd.) ... 9 parts by mass ・ Surfactant (Dega Nippon Ink Co., Ltd., Megafac F-177)                                                       ... 0.1 parts by mass ・ Methyl ethyl ketone ・ ・ ・ 130 parts by mass ・ Toluene: 35 parts by mass ・ Cyclohexanone: 20 parts by mass ・ Dimethylformamide: 20 parts by mass

[0149] Coating liquid for second layer of image receiving layer: ・ Methyl methacrylate / ethyl acrylate / methacrylic acid copolymer (Mitsubishi -Yeon Co., Ltd., Dinal BR-77) ... 17 parts by mass ・ Alkyl acrylate / alkyl methacrylate copolymer (Mitsubishi Rayon Co., Ltd. ), Dinal BR-64) ... 17 parts by mass -Pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., A-TMM T) ・ ・ ・ 22 parts by mass ・ Surfactant (Dega Nippon Ink Co., Ltd., Megafac F-177)                                                       ... 0.4 parts by mass ・ Methyl ethyl ketone ・ ・ ・ 100 parts by mass ・ Hydroquinone monomethyl ether ・ ・ ・ 0.05 parts by mass ・ 2,2-Dimethoxy-2-phenylacetophenone (photopolymerization initiator)                                                       ... 1.5 parts by mass

Using a 100-μm-thick polyethylene terephthalate (PET) film as a support, a coating solution for the first layer of the image receiving layer was applied using a spin coater (Whorer), and the coating was performed in an oven at 100 ° C. for 2 minutes. It dried and formed the image receiving layer 1st layer. The thickness of the obtained first image receiving layer is 1
was μm. On the formed image receiving layer first layer, the coating solution for the image receiving layer second layer is applied and dried by the same method, and an image receiving layer second layer having a film thickness of 26 μm is laminated to prepare an image receiving material. did.

[Image formation] The colored photosensitive layer of the above-prepared black photosensitive material was prepared using a corresponding color separation mask,
Ultra-high pressure mercury lamp (2kW, Dainippon Screen P-6
47-GA) imagewise exposure from the adjacent layer side (adhesive layer side) (latent image forming step).

Next, the surface of the adhesive layer of the photosensitive material and the surface of the image receiving layer of the image receiving material were brought into contact with each other and heated and pressed to bond them (laminating step). Lamination was performed with a Fuji Color Art Laminator at a speed of 900 mm / min. The temperature of the heating roller at this time was 125 ° C.

Next, the support of the black color photosensitive material was
When peeling development was performed at a peeling speed of 3000 mm / min so as to be folded back at 80 °, a black image was formed on the image receiving material so that the exposed portion was colored (image forming step).

For cyan, the latent image forming process was started in the same manner as above after the black latent image forming process was completed.
After the black image forming step was completed, a cyan image was formed by performing a laminating step and an image forming step using the image receiving material on which the black image was formed. Similarly, for the magenta color, after the completion of the cyan latent image forming step, the magenta latent image forming step was started and the subsequent steps were performed. In the same manner for yellow color, a full color image was obtained on the image receiving material. The image side of this image is overlaid on art paper and the color is 450 mm / min. The sheets were laminated by heating and pressing at a speed of 1, the whole surface was exposed from the image receiving material side with an ultrahigh pressure mercury lamp, and finally the support of the image receiving material was peeled off to obtain a full-color image on the art paper.

According to the method as described above, an image can be formed in a shorter time than in the conventional case, and the formed image has a sufficient quality as a surprint image for print proofing.

[0156]

According to the image forming method of the present invention, it is possible to form a high quality image which is dry and has excellent resolution and halftone dot reproducibility in a simple process efficiently and in a short time.

[Brief description of drawings]

FIG. 1 is a process explanatory diagram of an image forming method of the present invention.

FIG. 2 is an explanatory diagram of a multicolor image formed by the image forming method of the present invention.

[Explanation of symbols]

11 ... Support 12 ... Colored photosensitive layer 13 ... Adjacent layer 14 ... Photosensitive material 15 ... Support 16 ... Image receiving layer 17 ... Image receiving material 18 ... Image 19 ... Adjacent layer 20 ... Image

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA01 AA02 AA04 AB09 AC08                       AD03 BC13 BC42 CA00 CC11                       DA01 FA19 FA24                 2H096 AA23 BA05 CA20 EA04 GA50

Claims (3)

[Claims] 1. A colored photosensitive layer containing an addition polymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator and a colorant on a support, and an adjacent layer adjacent to the colored photosensitive layer. A latent image forming step of forming a latent image by imagewise exposing the colored photosensitive layer of a photosensitive material which is sequentially provided from the support side, and heating the photosensitive material on which the latent image is formed and the image receiving material in contact with each other. And / or a laminating step of applying pressure, and an image forming step of separating the photosensitive material and the image receiving material, transferring at least the colored photosensitive layer of the exposed portion to the image receiving material, and forming an image on the image receiving material. An image forming method comprising: a latent image forming step, a laminating step, and an image forming step are repeated twice or more using the same image receiving material to form a multicolor image. . 2. The image according to claim 1, wherein the Nth latent image forming step, which is the second or subsequent latent image forming step, is started at least before the end of the (N−1) th image forming step. Forming method. 3. In the latent image forming step, the exposure is 450 n.
The image forming method according to claim 1, wherein the image forming method is performed using a laser beam having a wavelength shorter than m.