JPS6169062A - Image forming method - Google Patents

Abstract

PURPOSE:To form a high-polymer compd. to a latent image forming part by exposing an image to a recording material formed by depositing a photosensitive silver salt, reducing agent and crosslinkable compd. and binder onto a base to form a latent image then heating uniformly the material. CONSTITUTION:The photosensitive silver salt, reducing agent, crosslinkable compd. and binder are deposited on the base to obtain the recording material. The image is exposed to such recording material to form the latent image and thereafter the recording material is substantially heated, by which the high-polymer compd. is formed to the part formed with the latent image of the photosensitive silver salt. The photosensitive silver salt is prepd. by mixing an aq. soln. of the alkaline metallic salt, alkaline earth metallic salt or ammonium salt of a long chain alipht. acid of >=10C and an aq. water soluble silver salt soln. The heating temp. after formation of the latent image is >=70 deg.C, preferably >=75 deg.C and more particularly preferably >=80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to an image forming method. Especially latent images? The present invention relates to a method for forming an image iron in which a polymer compound is formed using heat in a portion where a silver salt is present.

"Prior Art" The present inventors have already attempted to utilize the high photosensitivity and durability of photosensitive silver salts to form polymeric compounds, particularly in the form of images. For example, details are given in Japanese Patent Publication No. 7-CO 07tA/, in which an exposed silver halide photographic emulsion is treated with an aqueous reducing agent solution in the presence of an addition-polymerizable compound, and reaction intermediates produced in the treatment process are It was intended to be used as a polymerization initiator.

"Problems to be Solved by the Invention" Conventionally, a polymer compound was selectively produced in the latent image area by carrying out the entire polymerization reaction at the same time as wet development, which required a development process. there were. In other words, a treatment process in a wet state was essential. Furthermore, this method generally requires a polymerization reaction time of about one minute at the earliest.

``Means for Solving the Problems'' The present invention involves forming a latent image on a recording material supported on a support containing a photosensitive silver salt, a reducing agent, a crosslinking compound, and a binder, and then forming a latent image on the recording material. By substantially uniformly heating the material, 1
This is an image forming method characterized by the formation of a polymer compound.

The 1dDry treatment of the present invention has a remarkable feature of formation of artillery. In particular, it is completely unexpected that the portions having latent images are selectively promoted during the time when the crosslinking or polymerization reaction is promoted by heating the system to a temperature above 2ro 0c.

The polymer compound generated by the reaction can be used for image formation, or the portion where the polymer compound has been generated or the portion where the polymer compound has not been generated can be transferred and used for image formation.

As the photosensitive silver salt, one that provides ffl image nucleus resistance due to exposure to light is used. That is, photosensitive silver salts are convenient;
Silver halides, organic acid silver, silver salts of these coexisting, etc. are convenient.

A latent image is an image-like change that occurs in a silver halide photographic emulsion due to the action of electromagnetic waves or particle beams and is normally invisible to the naked eye, but becomes a visible image when developed. It is. In emulsions that produce normal negative images, IW images are produced by the generation of development nuclei in the silver halide grains when irradiated with electromagnetic waves or particle beams, whereas in direct positive emulsions, development nuclei that were originally present in all grains are generated. disappears due to irradiation, so f
A image is produced.

The photosensitive silver salt used in the present invention, such as a silver halide photographic emulsion, is a conventional silver halide emulsion that produces development nuclei in the irradiated area due to the action of electromagnetic waves or particle beams, that is, a negative image is produced during development. Silver halide photographic emulsions can also be used, and so-called direct positive emulsions can also be used, in which a greater number of development nuclei are present in silver halide grains in areas other than those exposed to image-like light irradiation. .

In the present invention, silver halide photographic emulsions used for ordinary development processing can be conveniently used as the silver halide photographic emulsion that produces negative image 2. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide photographic emulsions can be used. The photographic emulsion used in the present invention can be subjected to chemical sensitization and optical sensitization that are applied to ordinary photographic emulsions. That is, as chemical sensitization, sulfur sensitization, noble metal sensitization, and reduction sensitization can be performed.

For optical sensitization, optical sensitizing dyes used in ordinary photography, such as cyanine dyes and merocyania dyes, are effective.

The emulsion used in the present invention may also contain stabilizers 2, such as those used in conventional photography.

The silver halogenide photographic emulsion that can be used in the present invention can be prepared by utilizing solarization, the Burschel effect, the Kleiden effect, and the Sabache effect.

The photographic emulsion mentioned above consists of a system in which silver halide grains are dispersed during melting of a polymeric substance, and gelatin is widely used as the polymeric substance, but other hydrophilic colloids are also used. Can be used.

Further, an organic acid (with limited salt content) can be used as a photosensitive silver salt.

The method for producing photosensitive silver salts is already well known, and is disclosed in Tokko Sho A J-Ari No. 21 and Tokko Sho 11-Jo4 Ayr.
Familiar with methods such as No.

Generally, alkali metal salts of long-chain aliphatic acids with carbon atoms of 70 or more, alkaline earth gold! It is prepared by mixing an aqueous solution of salt A or ammonium salt with water (a silver salt aqueous solution). can coexist.

As the reducing agent, "Hymonium compounds, namely resorcinols, m-amine phenols, m-] diamines, j-pyrazolones, phenols, p-alkoxyphenols, and aminonaphthols" are used as reducing agents. and naphthalene-diols, etc. Specific examples of these include phloroglycine, m-aminephenol, m-aminephenol,
-dimethylaminophenol, 31tA-dimethyl-yo-pyrazolone, J-methyl-Hiro-hydroxyethyl-yo-pyrazolone, ' + 3 amethyl-μm hydroxyethyl-j-pyrazolone, p-methoxyphenol, β
-acetylphenylhydrazine, /-aryl-J-methyl-j-pyrazolone, 1,3-naphthalenediol, and the like. If necessary, two or more of these may be used in combination. The amount added to these silver salts is 0.0/
A percentage of IO to 300 mole percent is advantageous. Moreover, the special public Sho 4L7-
It is also advantageous to use these reducing agents in combination with ordinary photographic agents, as described in 207 Kol.

Common phenomena drugs (e.g. compounds according to Kendall's rules - hydroquinone, pyrocarol, catechol, ≠
-amino-7-naphthol, ≠-aminophenol,
(naphthohydroquinone, phenylpyranolidone, etc.), the amount of these added can be varied widely within a range that does not affect the weighting reaction. For example, 7 (7-6 to 10-2 mole percent, especially 7
(7-5 to l□-2 mole percent is advantageously used.

Examples of the crosslinkable compound include addition polymerizable compounds and polymers having the above-mentioned reducing agent layer t.

First, as the addition polymerizable compound, a compound having at least i vinyl or vinylidene groups, preferably a plurality of vinyl or vinylidene groups, can be used. There are no particular restrictions on these compounds, but compounds with a boiling point of to'c or higher are particularly convenient from the point of view of handling. Examples of these are 1', Yua, 2, □2, 2,
7, ethers, vinyl esters, and derivatives thereof. Specific examples include acrylic acid, sodium acrylate, calcium acrylate, barium acrylate, acrylamide, acryloylmol 7-olin, t-butyl acrylamide, dia-7ton acrylamide, ethyl acrylate, butyl acrylate, and hydroxyethyl. , acrylate, glycidyl acrylate, 3-chloro1-2-hydroxy-propyl acrylate, ethylhexyfluacrylate, lauryl acrylate, methyl methacrylate, methacrylamide, methacryloylanilide, β-hydroxypropyl methacrylate, etc. acids and their derivatives, styrene,
α-methylstyrene, vinyltoluene, chlorstyrene, methoxystyrene, vinylphenol, chloromethylstyrene/, vinylimidazole, vinylmethylimidazole, vinylpyridine, vinylmethylpyridine/, vinylmethylimidazole, p-toluenesulfone), vinyl Pyrrolidone, vinyl isopropyl ether, vinyl chloroethyl ether, vinyl benzyl ether, vinyl monoacid, notylene bisacrylamide, ethylenediamine diacrylamide, phenylene diacrylamide, xylylene diacrylamide, triaminohexane triacrylamide, triacryloyl triazine ,
Ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene oxide dimethacrylate, ethylene glycol acrylbate, ethylene glycol dicrotonate, pentaerythritol triacrylate, pentaerythritol IJ methacrylate and addition polymerizable Polymer compounds having a curvature (for example, acrylic acid or methacrylic acid derivatives of polymer compounds having a hydroxyl group, an amide group, an epoxy group, or an acid anhydride group) can be used. Two or more types of these can be used as necessary. Addition-polymerizable monomers/bodies lacking groups such as an azo group, an azomethine group, an active methyl group, and an active methylene group can also be used as needed.

Polymers of monomers having the above-mentioned base agent skeletons, such as m-acrylaminophenol, m-hydroxyphenoxyethyl acrylate, l-β-methacrylaminoethyl-3-methyl-j-pyrazolone, etc. It can be used as a polymer crosslinking resistant compound. In that case, the reducing agent and the crosslinking compound are busy working together.

In addition, depending on the sensitive wavelength range of the photosensitive silver salt, it is necessary to take a photo to obtain an image! (c) Couplers known in the industry and addition-polymerizable coupler ligatures can also be used together.

These have a polydispersity percentage of 0.06 to /λ00 relative to the silver salt, especially! Naishiri! O weight percent can be used.

Further, when using an organic silver salt, it is convenient to use an organic or inorganic halide in combination.

Examples of these include ammonium salts, alkyl halides, aryl halides, etc., and nolides include bromine, iodine, chlorine, etc. Two or more of these may be used in combination, if necessary.

Also, silver salt! 2 yuan? The ilJ, heptad Ml compound, additives, etc. can be molded onto the support in one layer or another. In that case, the polymer compound can be used as a binder if necessary.

Examples of the support include metal plates such as lead and aluminum, plastic films such as triacetylcellulose and polyethylene terephthalate, glass, paper, and resin-coated paper.

High polymer compounds for binders include gelatin, hydroxyethylcellulose, methylcellulose, and carbomethoxycellulose, which are superior in terms of image clarity, which is thought to be due to the support of 1,000f (↑e2oo seconds or more) or thermal conductivity. , Knife / Natural product molecular compound or synthetic polymer compound of polyvinyl butyral, polyvinyl alcohol, polyvinyl benzal, polyvinyl pyrrolidone, polyvinyl methyl imidazole, polyhydroxyethyl acrylate, two or more types are used as necessary I don't mind that.

In particular, polymeric compounds having an amide group are preferable.
7. body? If used, the binder game can be omitted.

In addition, if necessary, antifogging agents, surfactant additives, photographic sensitizers, stabilizers, thickeners, anti-setting agents, plasticizers, dyes, alkali generation + jiJ, water release agents, or pigments may be added. etc. can also be added.

When these are used in layers, the thickness of the coating layer is o, oo
It can be changed arbitrarily within the range of IQ or IQ.

Further, during coating, an undercoat layer, a protective layer, etc. can be provided according to a conventional method.゛) Heat conductivity during heating,
In order to prevent the recording layer from sticking to the heating section, it is preferable to have a protective layer. Also, 1M colored under the layer where the polymer compound is formed? (If provided, there is an advantage that the colored layer can be visualized in image form.

In the present invention, various exposure means can be used. The latent image is obtained by a single beam exposure to radiation, including visible light. Commonly used light sources include sunlight, strobes, flat lights, Kungesten lamps, mercury lamps,
It can be used as a light source for iodine lamps, etc.), Roken lamps, xenon lamps, laser beams, CRT light sources, plasma light sources, fluorescent tubes, light emitting diodes, etc.

It is also possible to use an LCD (liquid crystal), PLZT (lanthanum-doped lead titanium zirconate), etc., and use a combination of a 9-micro shutter array and a linear light source or a planar light source in the 7Cu light means.

The type of light source and the amount of exposure can be appropriately selected depending on the wavelength and sensitivity of the photosensitive silver salt.

In the present invention, the heating temperature is 7(:)'C or higher, preferably 7J0C or higher, particularly r00C or higher. ts'C
However, although images can be obtained by heating for a long time, they are not clear and have poor operability, making them undesirable as an image forming method.

The method of the present invention will be specifically described below using Examples, but these are of course examples within the scope of the idea and technical field of the present invention, and the application of the present invention is not limited to these. It's not something you can do.

Example 1. 15 Apply the following solution on the polyethylene terephthalate film using a coating rod No. 20, and
It was dried by wind blowing at 'C.

methanol 20rrt1% polyvinylpyrrolid 731,
Acrylamide 27, methylene his-acrylamide 0.23? , and 1 mole of behenic acid and 81 moles of silver nitrate/, 4tμ? Consisting of ￥
1a0 Then 1m-dimethylaminophenol 137■, ammonium bromide 2. jm9 and ammonium iodide 0
．． I took a bath on λmy ligment memenor jrrtl and applied one liquid to it.

After drying, Hirochiselatin, 7% sodium lawalylbenzenesulfonate, formaldehyde bisulfite l-
IJumfA/θθ1.11.0, θ0/Y, respectively
The solution was applied and dried.

In this way, half of the 1ζ recording material is placed on black paper.
Exposure was carried out for 1 second from a distance of /m from the OW light bulb to form an m-image nuclear ligation at the - tip. When this nine was combined and printed out, no black spots were observed in the exposed areas. Then, this recording material was sandwiched between flat heating plates kept at 0°C or 0°C. After keeping it warm for about 30 seconds, it was thoroughly rinsed in a methanol bath. In both cases, only the exposed areas remained as a strong film, confirming that the polymerization reaction was occurring selectively. If the heating temperature resistance is set to bj0c, the heating time t
An image was obtained only in one case after applying it to the skin for about 3 minutes.

A recording material was prepared in the same manner as in Example 1, except that it was mixed with m-dimethylaminephenol-resistant polyvinylpyrrolidone, etc., and removed with ceratin, and was tested in the same manner as in Example 1. I did it. In both cases, good film relaxation was obtained in the 8-light area.

Example 3 f゛ The same operations as in Example 3 were carried out except that Ho-Arpcht sodium sulfite salt θ, 001, fpm-dimethylamine phenol, etc. were used in combination.

Good results were also obtained in this case. Almost the same results as in Example 1 were obtained when formaldehyde, bisulfite yo, and ott were used.

Example Gubenzaldehyde or cyclohexanone bisulfite 1
The same operating resistance as in Example 3 was achieved using formaldehyde bisulfite spray.

Good results similar to those in Example 1 were obtained.

Example Examples of use in combination with reduction resistance agents for ordinary photographic developers are of course shown.

/-Phenyl-3-virazolidone/m-dimethylaminophenol The same procedure as in Example μ was carried out using tl loading percentages of o and i.

However, the exposure time was 30 seconds. In this case, similar results were obtained. Similar results were obtained when 0.01 weight percent of catechol was used in the /-722-3-pyrazolidone base.

Example 4: G-nylon versus polyvinylpyrrolidone
The same procedure as in Example 1 was carried out except that 0 weight cents was used. It was found that when the heating temperature was set to 110C to 100C and maintained for about 20 seconds, a bright molecular compound was produced only in the exposed areas.

Example 7 Tetraethylene glycol dimethacrylate l.

7m1. Polyvinylpyrrolidone (K-tao, )
J.

oy, @salt θ of behenic acid, ritl, sulfite aqueous sodium aldehyde adduct o, ooiy, and zinc oxide O1
≠ Rinashi/, 739 with methanol i0m! , the VC government was divided. This was coated on a polymer support using Coating Ronde λO, and dried by heating. Then, m-dimethylaminephenol j00m9, catechol o, oti
-rtv;), odor f Hianmonium IO to 20m
9, and ammonium iodide 0. J or 1 mg2 methanol-k s rat K (f4) Apply with a filtered liquid,
It was heated and dried.

Furthermore, the surface was moistened with a solution consisting of 1 ornl of tizelatin and /% laurylbenzene sulfur/sodium acid/rnl, and then dried. Example! After exposure in the same manner as in Example t, the same post-treatment as in Example t was performed. ! o 'C or go
Clear images were obtained in both cases by rinsing in warm water. The same result was obtained using a methanol bath.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1. Display of incidents Showa! 1st patent application 1333
No. 2, Title of the invention Image forming method 3, Relationship with the case of the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of the amendment Column 5 of the "Detailed Description of the Invention" in the specification The statement in the "Detailed Description of the Invention" section of the Description of Contents of the Amendment is amended as follows.

From the ``said patent'' on the second line of page 6 to the ``diols'' on the 6th line of the same page, there are ``Japanese Patent Publication No. 11149/1983 (resorcinols), Japanese Patent Publication No. 6581/1986 (m-aminophenols). , Special Publication No. 47-14667 (5-pyrazolones), Special Publication No. 14667 (5-pyrazolones)
-14668 (alkylphenols), Special Publication No. 14668 (Sho 47)
-14669 (Alkoxynaphthols), Special Publication No. 4
No. 7-20741 (m-phenylenediamines), Special Publication No. 1569 (1972) (Naphthols), Special Publication No. 1987 (1983)
Compounds described in No. 0697 (hydrazines), or JP-A-57-138632, JP-A-57-24263
No. 8, JP 5757-176O33, U.S. Patent No. 35
85030".

Procedural amendment document February 9, 1985, Palace of the Director-General of the Licensing Agency 1, Indication of the case Showa! Patent Application No. 1yi3j3
No. 2, Name of the invention Image forming method 3, Relationship with the case of the person making the amendment Patent owner 1 person Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address 106 Higashij:
(2-1'1126 Nishi-Azabu, Minato-ku;) No. 0 Fuji Photo Film Co., Ltd. Tokyo Head Office Tel: (406) 2537 Table Subject of amendment Column 5 of "Detailed Description of the Invention" of the description, Description of the contents of the amendment The description in the "Detailed Description of the Invention" section is amended as follows.

(11th page 14/-th line "Formaldehyde, bisulfite" "Formaldehyde bisulfite" and correct it.

(2) On page 16, line 3, after "Results obtained." [The mechanical strength of the film remaining after the wash-off is stronger when formaldehyde bisulfite is used than when it is not used. The strength was approximately dependent on the amount of formaldehyde bisulfite. ” is inserted.

1965, month, day

Claims (1)

[Claims] A recording material carrying a photosensitive silver salt, a reducing agent, a crosslinkable compound, and a binder on a support is imagewise exposed to form a latent image, and then the recording material is heated substantially uniformly to make the recording material photosensitive. An image forming method characterized by forming a polymer compound in the area where a latent image of silver salt is formed.