JPH0623847B2 - Transfer image forming method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a transfer image forming method using an image receiving material.

BACKGROUND OF THE INVENTION An image forming method using a light-sensitive material having a light-sensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support is described in JP-B-45-11149 and 47-20741.
No. 49-10697, JP-A-57-138632.
No. 58-169143.
In these methods, when the exposed silver halide is developed using a developer, a coexisting polymerizable compound (eg, vinyl compound) initiates polymerization to form an image-like polymer compound. Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

The present inventors attempted to improve the above method and invented a method capable of forming a polymer compound by a dry treatment, and the present invention has been applied for a patent (Japanese Patent Application No. 59-1913).
53). This method uses a photosensitive silver salt (silver halide),
By subjecting a recording material (photosensitive material) having a photosensitive layer composed of a reducing agent, a crosslinkable compound (polymerizable compound) and a binder supported on a support to imagewise exposure to form a latent image, and then thermally developing it. The polymer compound is formed in the portion where the latent image of the photosensitive silver salt is formed.

These image forming methods are methods in which the polymerizable compound in the portion where the latent image of silver halide is formed is polymerized. The present inventors have further invented a method capable of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed, and this invention has already been applied for a patent (Japanese Patent Application No. 60-
210657). This method, by heating,
The reducing agent acts on the portion where the latent image of silver halide is formed to suppress the polymerization of the polymerizable compound and at the same time promotes the polymerization of other portions.

As one aspect of the image forming method as described above, a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support, at the same time as imagewise exposure, or after imagewise exposure, There is an image forming method in which an unpolymerized polymerizable compound is transferred to an image receiving material by performing development processing and applying pressure in a state where the image receiving material is superposed on the developed photosensitive material. According to this image forming method, a clear image can be obtained on the image receiving material, but there is also a tendency that the image gradually becomes blurred depending on storage conditions and the like.

SUMMARY OF THE INVENTION An object of the present invention is to provide a transfer image forming method in which a transferred image retains its sharpness even after being stored for a long period of time or under severe conditions.

In the present invention, a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support is imagewise exposed to form a latent image of silver halide, and at the same time as the imagewise exposure, Alternatively, after the imagewise exposure,
A heat development treatment is carried out by heating at 0 to 200 ° C. for 1 second to 5 minutes, whereby the polymerizable compound in the portion where the latent image is formed (or the portion where the latent image is not formed) is polymerized, and the heat development treatment is carried out. By pressing the image-receiving material having the image-receiving layer containing a thermal polymerization initiator on the support, the unpolymerized polymerizable compound was transferred to the image-receiving material, and the image-receiving material The present invention provides a transfer image forming method, which comprises heating the film at 50 to 250 ° C. for 0.1 to 100 seconds.

EFFECTS OF THE INVENTION The transfer image forming method of the present invention is characterized in that the image receiving layer of the image receiving material contains a thermal polymerization initiator.

According to the study by the present inventors, in the image forming method as described above, since the unpolymerized polymerizable compound contained in the image transferred onto the image receiving material is in a liquid state, it gradually diffuses to the surroundings to form an image. Was blurred and the sharpness was lowered.

By forming a transferred image on the image-receiving material of the present invention and heating the image-receiving material, the unpolymerized polymerizable compound is cured, so that the above-mentioned problem of storability is solved. Therefore, the image obtained on the image-receiving material of the present invention retains its sharpness even after long-term storage or storage under severe conditions.

DETAILED DESCRIPTION OF THE INVENTION The thermal polymerization initiator used in the image-receiving material of the present invention is a compound that generally undergoes thermal decomposition under heating to generate a polymerization initiation species (particularly a radical), and is usually used as an initiator for radical polymerization. It is what Regarding the thermal polymerization initiator, "Additional Polymerization / Ring-Opening Polymerization" edited by the Society of Polymer Science, Polymeric Experiments Editorial Committee 1
983, Kyoritsu Shuppan), pp. 6-18. As the thermal polymerization initiator, organic peroxides such as diacyl peroxide, ketone peroxide, peroxydicarbonate, alkyl peroxide, alkylhydroperoxide and sulfonyl peroxide; inorganic peroxides And organic compounds other than peroxides.

Specific examples of the organic peroxides include benzoyl peroxide, di-t-peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide and the like. Specific examples of the inorganic peroxides include hydrogen peroxide, potassium persulfate, ammonium persulfate, and perborate.
Specific examples of organic compounds other than peroxides include azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, and 2,2. -Azobis (2-methylbutyronitrile), azobisdimethylvaleronitrile,
2,2'-azobis (2-amidinopropane) hydrochloride,
Azo compounds such as sodium azobiscyanovalerate, p-
Examples thereof include sodium toluenesulfinate, bisazide, diazo compounds and the like. Among these, azo compounds are particularly preferable.

In the image receiving material of the present invention, the image receiving layer preferably contains the thermal polymerization initiator in the range of 0.1 to 5000 mg / m ² , and more preferably 1 to 1000 mg / m ² .

The image-receiving layer of the image-receiving material of the present invention preferably contains a binder. The binder that can be used in the image receiving material of the present invention can be contained in the image receiving layer alone or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and examples thereof include proteins such as gelatin, gelatin derivatives, and cellulose derivatives, natural substances such as starch and polysaccharides such as arabic gum, polyvinyl alcohol, and polyvinyl alcohol. Includes synthetic polymeric materials such as water soluble polyvinyl compounds such as pyrrolidone, acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds that increase the dimensional stability of the image receiving material in the form of a latex.

The binder is 0.01 g in the image receiving layer of the image receiving material.
/ M ^{2 to} 100 / m ² is preferably used.
A more preferable range of use is 0.1 g / m ^{2 to} 10 g / m ²
Is.

The image-receiving layer of the image-receiving material of the present invention may contain any other component besides the binder. For example, when a color-developing system composed of a color-developing agent and a color-developing agent is used as a color-developing system for an image, the image-receiving layer may contain the color-developing agent. Further, the image receiving layer can be configured as a layer containing a mordant. The mordant can be selected from compounds known in the photographic art and used. If necessary, a plurality of mordants having different mordant strengths may be used to form the image-receiving layer in two or more layers.

The layer thickness of the image receiving layer is preferably 1 to 100 μm, and more preferably 1 to 20 μm.
A protective layer may be further provided on the image receiving layer.

The image-receiving material of the present invention comprises a support and an image-receiving layer containing the above thermal polymerization initiator. Materials that can be used for the support include glass, paper, woodfree paper,
Coated paper, cast coated paper, baryta paper, synthetic paper, metal and its analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate and other films, and resin materials and polyethylene and other polymers for lamination It is possible to cite the paper etc.

The image-receiving material of the present invention can be produced by various methods. Generally, the components of the image-receiving layer containing a thermal polymerization initiator are dissolved, emulsified or dispersed in a suitable solvent to prepare a coating solution. Then, this coating solution can be easily obtained by applying it to the support as described above and drying.

Hereinafter, a method of using the image receiving material of the present invention will be described.

The image receiving material of the present invention can be used in an image forming method for forming a transferred image containing a polymerizable compound on the image receiving material. That is, by forming an image containing a polymerizable compound on the image-receiving material of the present invention and then heating the image-receiving material, the sharpness of the transferred image with time can be improved.

As a method of heating the image receiving material on which an image is formed, a conventionally known method can be used.

For example, the photosensitive material may be brought into direct contact with a hot plate such as a hot plate or a drum, or may be heated while being conveyed using a heat roller.

It is also possible to use air heated to a high temperature, or to heat by high frequency heating or a laser beam. Infrared heaters may also be used to heat depending on the nature of the imaged material. Further, a method of heating by utilizing overcurrent generated by electromagnetic induction can be applied.

Further, the material on which the image is formed may be heated in a bath in which an inert liquid, for example, a fluorine-based liquid is heated.

Further, in addition to the above-mentioned heating means, the image receiving material may be provided with a heating source for heating. For example, a layer of conductive particles such as carbon black or graphite may be placed in the image receiving material and Joule heat generated when electricity is applied may be used.

Generally, the heating temperature is preferably 50 ° C to 250 ° C, more preferably 80 ° C to 250 ° C.
The heating time is generally 0.1 second to 100 seconds, more preferably 1 second to 50 seconds.

When the substance forming the formed image is easily affected by air oxidation, it is effective to perform degassing or replacement with an inert gas around the heating portion during heating. When the surface of the image receiving material on which an image is formed is heated to the air side, a method of preventing evaporation of moisture and volatile components and attaching a cover to the surface of the material for heating purposes is also effective.

As an example of an image forming method for forming a transfer image containing a polymerizable compound on an image receiving material, silver halide on a support,
A light-sensitive material having a light-sensitive layer containing a reducing agent and a polymerizable compound is imagewise exposed to form a latent image of silver halide, and development processing is performed simultaneously with or after imagewise exposure. By polymerizing the polymerizable compound in the area where the latent image is formed (or in the area where the latent image is not formed) and applying pressure in the state where the image receiving material is superposed on the developed photosensitive material, unpolymerized polymerization Examples of the method include transferring a polymerizable compound to an image receiving material.

Hereinafter, imagewise exposure, development treatment in the above image forming method,
The transfer of the unpolymerized polymerizable compound to the image receiving material will be described.

As the exposure method in imagewise exposure, various exposure means can be used, but generally, a latent image of silver halide is obtained by imagewise exposure of radiation including visible light. The type of light source and the amount of exposure can be selected according to the photosensitive wavelength of silver halide (wavelength sensitized when dye sensitization is performed) and sensitivity. The original image may be a monochrome image or a color image.

The transfer image forming method of the present invention comprises:
Alternatively, after imagewise exposure, heat development processing is performed. Since the heat development process is a dry process, it has advantages that the operation is simple and the process can be performed in a short time.

As a heating method in the heat development treatment, various conventionally known methods can be used. Also, Japanese Patent Application Sho 60-
As in the light-sensitive material described in the specification of No. 135568, a heat-generating layer may be provided on the light-sensitive material and used as a heating means. The heating temperature is generally 80 ° C to 200 ° C, preferably 100 ° C to 160 ° C. The heating time is generally 1 second to 5 minutes, preferably 5 seconds to 1 minute.

In the image forming method described above, the developing treatment is performed as described above to polymerize the polymerizable compound in any portion of the portion where the latent image of silver halide is formed or the portion where the latent image is not formed. In this image forming method, the polymerizable compound in the portion where the latent image of silver halide is formed is generally polymerized in the above-mentioned developing treatment, but as described above, it is described in Japanese Patent Application No. 60-21065. By adjusting the type and amount of the reducing agent used in the light-sensitive material as in the light-sensitive material, it is possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed.

In the image forming method described above, the unpolymerized polymerizable compound is transferred to the image receiving material by pressing the image receiving material in a state of being superposed on the photosensitive material which has been subjected to the development processing as described above. You can get the image. Various conventionally known methods can be used for the pressing means. Further, a general image forming method using an image receiving element such as an image receiving material is described in Japanese Patent Application No. 60-112284.

Further, using a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent, a polymerizable compound, and a color image forming substance on a support, the development treatment is performed as described above to polymerize and cure the polymerizable compound. , Thereby immobilizing the color image forming substance in the cured portion, and then applying pressure in a state in which the image receiving material is superposed on the light-sensitive material in which the color image forming substance in the cured portion is immobilized. The forming substance can be transferred to the image receiving material. An image forming method for forming a color image on an image receiving material using a light-sensitive material containing a color image forming substance as described above is also described in Japanese Patent Application No. 60-121284.

An image forming method which can use the image receiving material of the present invention,
Regarding the light-sensitive material that can be used in the image forming method, in addition to the application specifications relating to the image forming method and the light-sensitive material described above, Japanese Patent Application Nos. 59-195407, 60-22980, and 60-29894, Same as 60-
68874, 60-117089, 60-13
No. 5568, No. 60-139746, No. 60-141
No. 799, No. 60-218603, No. 60-2260.
No. 84, No. 60-227527, No. 60-22752.
No. 8, No. 60-261887, No. 60-261888
No. 60-294337, No. 60-294338
No. 60-294339, No. 60-294340
No. 60, No. 60-294341, No. 61-3024, No. 61-3025, No. 61-5750, No. 61-57.
No. 51, No. 61-11556, No. 61-11557
No. 61-13181, No. 61-20438, No. 61-25576, No. 61-25577, No. 61-
No. 25578, "Image forming method" filed on February 13, 1986 by the applicant, "Photosensitive material" filed on February 24, 1986 by the applicant (2), (3) and (4). , Application filed on February 26, 1986 by the applicant (2)
And (3) "Photosensitive material", 1986 by the applicant
March 10th, Application (1), (2), (3), (4),
(5), (7) and (8) "Photosensitive microcapsules and photosensitive materials", March 1, 1986 by the present applicant.
"Photosensitive material" of 0 days application (6), (10), (11),
It is described in each specification of “Image forming method and image receiving material” of the applicant (9) filed on Mar. 10, 1986 by the present applicant.

The image receiving material of the present invention and the image forming method using the same are
Black and white or color imaging and printing, printing, printing plates, X-ray imaging, medical diagnostic imaging (for example, ultrasonic diagnostic machine C
It can be applied to many fields such as RT photographing), computer graphic hard copy, and copying machine.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Example 1] Preparation of image receiving material To 125 g of water, 11 g of 40% aqueous sodium hexametaphosphate solution was added, and further 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were mixed, and mixed. Coarsely dispersed. The liquid was further dispersed with a Dynamill disperser to obtain 200
To 50 g, 6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added and mixed uniformly. 2 g of the following thermal polymerization initiator was added to this mixed solution to prepare a coating solution.

(Thermal polymerization initiator) This coating solution was applied uniformly onto art paper having a weight of 43 g / m ² so as to give a wet film thickness of 30 μm, and then dried to prepare an image receiving material according to the present invention.

Preparation of Silver Halide Emulsion 600 m of an aqueous solution containing 21 g of sodium chloride and 56 g of potassium bromide in an aqueous solution of gelatin (containing 20 g of gelatin and 3 g of sodium chloride in 1000 m of water and kept at 75 ° C.) while stirring (an aqueous solution of silver nitrate ( Water 600m
4) simultaneously dissolving 0.59 mol of silver nitrate)
Added at equal flow rate over 0 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μm was prepared.

After washing the above emulsion with water to desalinate it, sodium thiosulfate 5
mg and 4-hydroxy-6-methyl-1,3,3a, 7-
20 mg of tetrazaindene was added and chemical sensitization was performed at 60 ° C. The yield of emulsion was 600 g.

Preparation of benzotriazole silver emulsion 28 g of gelatin and 13.2 g of benzotriazole were added to 3 parts of water.
It was melted in 000m. The solution was stirred while maintaining the temperature at 40 ° C., and a solution prepared by dissolving 17 g of silver nitrate in 100 m of water was added over 2 minutes.

By adjusting the pH of the resulting emulsion, excess salt is precipitated,
Removed. Then, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion. The yield of emulsion was 400 g.

Preparation of Photosensitive Composition To 15 g of trimethylolpropane triacrylate, 0.06 g of a copolymer represented by the following formula, Pergascript Red I-6-B (manufactured by Ciba Geigy) 0.9.
g, a hydrazine derivative represented by the following formula (reducing agent)
1.07 g and 1.07 g of a developing agent (reducing agent) represented by the following formula were dissolved. To this solution was added 3.5 g of silver halide emulsion, 3.5 g of benzotriazole silver emulsion, prepared as described above, and Emarex NP-8.
A solution prepared by dissolving and mixing 0.3 g (manufactured by Nippon Emulsion Co., Ltd.) was added, and a homogenizer was used for 15 minutes at 40 ° C. for 15 minutes.
It was emulsified and dispersed at 000 rpm to prepare a photosensitive composition.

(Copolymer) (Hydrazine derivative) (Developer) Preparation of microcapsule solution A mixed solution of 8.2 g of 20% aqueous solution of Isoban (manufactured by Kuraray Co., Ltd.) and 39 g of 3% aqueous solution of pectin was adjusted to pH 4,
Add the entire amount of the photosensitive composition prepared as described above,
Using homogenizer at 40 ℃ for 2 minutes at 7000 rpm
And emulsified and dispersed.

To 55 g of this emulsion, 6 g of 40% aqueous solution of urea, 2.5 g of 10% aqueous solution of resorcin and 8 g of 30% aqueous solution of formalin were sequentially added, and the mixture was heated and stirred at 60 ° C. for 2 hours at 1000 rpm to prepare a microcapsule solution. .

Preparation of photosensitive material 10 g of microcapsule liquid prepared as described above
Then, 0.8 g of a 20% triethanolamine aqueous solution was added to prepare a coating solution. This coating solution was applied onto a polyethylene terephthalate film so as to have a wet film thickness of 50 μm and dried to prepare a photosensitive material.

Image formation and its evaluation The light-sensitive material obtained as described above was exposed with a tungsten bulb at 200 lux for 1 second through a line drawing original having a width of 100 μm, and then heated on a hot plate heated to 125 ° C. for 10 seconds. did.

Then, the light-sensitive material and the image-receiving material obtained as described above were overlapped and passed through a 350 Kg / cm ² pressure roller, and a clear positive magenta image with gradation corresponding to the unexposed area was received. Obtained on the material.

The image receiving material was heated at 140 ° C. for 20 seconds.

The image thus obtained on the image receiving material is 60
Even after being left for a day, the line width of 100 μm was maintained and the image was stable.

[Example 2] Preparation of image-receiving material In the same manner as in Example 1 except that the same amount of the following thermal polymerization initiator was used instead of 2 g of the thermal polymerization initiator used in the preparation of the image-receiving material of Example 1. An image receiving material according to the present invention was prepared.

Image formation and evaluation thereof An image was formed on the image receiving material by performing the same processing as in Example 1 except that the image receiving material prepared as described above was used.

The image receiving material was heated at 140 ° C. for 10 seconds.

The image thus obtained on the image receiving material is 60
Even after being left for a day, the line width of 100 μm was maintained and the image was stable.

As is clear from the results of Examples 1 and 2, the images obtained on the image receiving material according to the present invention retain their sharpness even after being stored for a long period of time.

Comparative Example 1 Preparation of Image Receiving Material An image receiving material for comparison was prepared in the same manner as in Example 1 except that the thermal polymerization initiator was not added in the preparation of the image receiving material of Example 1.

Image formation and evaluation thereof An image was formed on the image receiving material by performing the same processing as in Example 1 except that the image receiving material prepared as described above was used.

The image receiving material was heated at 140 ° C. for 10 seconds.

When the image obtained on the image receiving material as described above was left for 60 days, the line width of 100 μm expanded to about 130 μm and the contour became slightly blurred.

Claims (12)

[Claims] 1. A photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support is imagewise exposed to form a latent image of silver halide, and simultaneously with the imagewise exposure. , Or after the imagewise exposure,
A heat development treatment is carried out by heating at 0 to 200 ° C. for 1 second to 5 minutes, thereby polymerizing the polymerizable compound in the portion where the latent image is formed, and the photosensitive material which has been subjected to the heat development treatment is placed on a support. The unpolymerized polymerizable compound is transferred to the image receiving material by pressurizing the image receiving material having the image receiving layer containing a thermal polymerization initiator in the superposed state, and the image receiving material is heated at 50 to 250 ° C. for 0.1 to A transfer image forming method characterized by heating for 100 seconds. 2. The transfer image forming method according to claim 1, wherein the thermal polymerization initiator is an azo compound. 3. The image receiving layer contains 1 to 10 thermal polymerization initiators.
The transfer image forming method according to claim 1, wherein the transfer image forming method is in the range of 00 mg / m ² . 4. The transfer image forming method according to claim 1, wherein the image receiving layer further contains a binder. 5. The transfer image forming method according to claim 1, wherein the image receiving layer has a layer thickness of 1 to 100 μm. 6. The heating temperature of the image receiving material is 80 to 20.
The transfer image forming method according to claim 1, which is 0 ° C. 7. A photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support is imagewise exposed to form a latent image of silver halide, and at the same time as the imagewise exposure. , Or after the imagewise exposure,
A heat development treatment is carried out by heating at 0 to 200 ° C. for 1 second to 5 minutes, thereby polymerizing the polymerizable compound in the portion where the latent image is not formed, and the heat-development-processed photosensitive material is provided with a support. The unpolymerized polymerizable compound is transferred to the image receiving material by pressing the image receiving material having the image receiving layer containing a thermal polymerization initiator in the superposed state, and the image receiving material is heated at 50 to 250 ° C. for 0.1 A method for forming a transfer image, which comprises heating for 100 seconds. 8. The transfer image forming method according to claim 7, wherein the thermal polymerization initiator is an azo compound. 9. The image-receiving layer contains 1 to 10 thermal polymerization initiators.
The transfer image forming method according to claim 7, wherein the transfer image forming method is in the range of 00 mg / m ² . 10. The transfer image forming method according to claim 7, wherein the image receiving layer further contains a binder. 11. The image-receiving layer has a layer thickness of 1 to 100 μm.
The transfer image forming method according to claim 7, wherein 12. A heating temperature of the image receiving material is 80 to 2
The transfer image forming method according to claim 7, wherein the temperature is 00 ° C.