JPH05181285A - Image forming method - Google Patents

Abstract

PURPOSE:To form an image by uniform heating for a relatively short time when a polymer image is formed with silver halide by heat development. CONSTITUTION:A photosensitive material obtd. by forming a photosensitive polymerizable layer 13 contg. silver halide, a reducing agent and a polymerizable compd. on a base 12 is exposed with image and the photosensitive polymerizable layer 13 is coated with a liq. 14 and covered with a sheet 15. The photosensitive material is then heated at >=60 deg.C, the silver halide is subjected to heat development and the polymerizable compd. is cured following the image to form a polymer image.

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 which forms an image by polymerizing a polymerizable compound by utilizing the photosensitivity of silver halide.

[0002]

A method of forming a polymer image by imagewise exposing a light-sensitive material containing a silver halide, a reducing agent and a polymerizable compound to develop the silver halide, thereby polymerizing the polymerizable compound in an image form. Japanese Patent Publication No. 45-11149 (US Pat. No. 3,697,275, West German Patent 172).
0665 and British patent 1131200)
It is described in. In this method, the polymerization is initiated by an oxidant radical of a reducing agent that has reduced silver halide (which may be a radical generated by decomposition of an oxidant of the reducing agent; hereinafter, simply referred to as oxidant radical). ..

On the other hand, a method of developing a silver halide by heating and forming a polymer image only by dry processing is disclosed in Japanese Patent Publication Nos. 3-12307 and 3-12308 (US Pat. No. 4,629,676 and European Patent Publication). No. 0174634A, each specification). In the method described in Japanese Patent Publication No. 3-12308, a photosensitive material containing a color image forming substance is used. Then, the polymerizable compound is polymerized in an image form, and then the uncured portion is removed to form a color image in the cured portion, or the uncured portion containing the color image forming substance is transferred to an image receiving material to receive an image. A color image is formed on the material.

It is known that in the heat development step of the image forming method as described above, oxygen in the air penetrates into the light-sensitive material and inhibits the polymerization reaction (oxygen has a polymerization inhibiting action). ing. Therefore, in order to prevent the polymerization inhibition effect of oxygen, many means have already been proposed. For example,
Japanese Examined Patent Publication No. 3-12308 and JP-A Nos. 62-210447 and 62-210461 disclose a method of performing heat development in a nitrogen atmosphere and a method of covering a photosensitive layer with a sheet and performing heat development. In addition, JP-A-2-1395
No. 62 (US Pat. No. 4,977,057),
A method is disclosed in which a liquid such as water is permeated into the photosensitive layer to perform heat development. Further, EP Patent Publication No. 0426192
The specification discloses a method in which polyvinyl alcohol having a high degree of saponification (having a function of blocking oxygen) is added to a light-sensitive material.

[0005]

By the way, the use of the above-mentioned light-sensitive material for producing a printing plate is disclosed in JP-A-64-17.
No. 047 and EP Patent Publication No. 0426192. The present inventors have particularly examined the method of using a light-sensitive material for producing a printing plate.
In this method, the polymer image formed on the light-sensitive material is used as a printing plate.
Compared with the method using the color image-forming substance described in JP-A-8, the strength of the polymer image is very important. A relatively long development time is required to obtain a strong polymer image. However, if the developing time is long, the effect of inhibiting the polymerization of oxygen in the air becomes large. Therefore, it is necessary to shut off oxygen in the air more strongly than before.

Therefore, the present inventors have examined various means for preventing the above-mentioned oxygen polymerization inhibiting action. The method of covering the photosensitive layer with a sheet and heat-development disclosed in JP-B Nos. 3-12308, 62-210447 and 62-210461 can be carried out very easily. However, when the present inventors applied this to the production of a printing plate, it was found that the blocking of oxygen was insufficient.
According to the research of the present inventor, even if the photosensitive layer is covered with a sheet,
A significant amount of air enters from the sides of the stack. In order to prevent this, of course, it is sufficient to cover the entire photosensitive material with a sheet, but this makes it difficult to continuously process a large amount of photosensitive material using an apparatus (which is indispensable for practical use). .. In the method disclosed in JP-A-2-139562 (U.S. Pat. No. 4,977,057) in which a liquid is permeated into a photosensitive layer to perform heat development, oxygen is considerably blocked. However, when the liquid is permeated into the photosensitive layer by coating or the like, the surface of the photosensitive layer becomes wet and sticky, which makes it difficult to handle the photosensitive material. In particular, when a photosensitive material is continuously processed using an apparatus, if the photosensitive layer adheres to a heating device or a conveying device, the processing becomes substantially impossible.

An object of the present invention is to provide a method of forming an image by heating a light-sensitive material from the air and heating it uniformly and for a relatively short time.

[0008]

The above object is to subject a photosensitive material, which has a photosensitive polymerizable layer containing a silver halide, a reducing agent and a polymerizable compound on a support, to imagewise exposure, A liquid is applied onto the polymerizable polymerizable layer, and the photosensitive polymerizable layer is covered with a sheet. In that state, the photosensitive material is heated at a temperature of 60 ° C. or higher to thermally develop the silver halide. Was imagewise cured to form a polymer image.

[0009]

The image forming method of the present invention is characterized in that a liquid is applied on the photosensitive polymerizable layer, the photosensitive polymerizable layer is covered with a sheet, and the photosensitive material is heated in that state. In the method of the present invention, the light-sensitive material is heated while being completely shielded from the air by combining the liquid and the sheet. Therefore, an image can be formed uniformly and by heating for a relatively short time. Further, since the photosensitive polymerizable layer coated with the liquid is further covered with a sheet, it is easy to handle the photosensitive material during heating. Further, even when the photosensitive material is continuously processed using the apparatus, the photosensitive polymerizable layer does not adhere to the heating apparatus or the conveying apparatus. Therefore, by using the method of the present invention, a large amount of light-sensitive material can be continuously processed by using the apparatus while preventing the polymerization inhibition effect of oxygen.

DETAILED DESCRIPTION OF THE INVENTION The preferred embodiments of the present invention are shown below.

(1) The liquid is a liquid which is inert to the photosensitive material. Hydrophilic (but excluding water) liquids are preferred. (2) The liquid forms a liquid film having a film thickness of 0.1 μm or more on the photosensitive polymerizable layer. (3) The photosensitive material is heated from the support side. (4) The photosensitive material is heated from the side of the photosensitive polymerizable layer. (5) The heating temperature is 100 ° C to 200 ° C. (6) The heating time is 1 second to 180 seconds.

The thermal development which is a feature of the present invention will be described. 1 and 2 are schematic sectional views showing the thermal development of the present invention. FIG. 1 shows the case where the photosensitive material is heated from the support side. In the method of the present invention, a photosensitive material provided with a photosensitive polymerizable layer (13) on a support (12) is used. After imagewise exposure, the liquid (14) is applied onto the photosensitive polymerizable layer (13). Further, the photosensitive polymerizable layer is covered with the sheet (15). As shown in FIG. 1, the laminate was heated on the hot plate (11) from the support (12) side to thermally develop the silver halide, and the polymerizable compound was imagewise cured to form a polymer image. Form. In addition, according to the method of the present invention, as shown in FIG.
As shown in, it is also possible to heat from the side of the photosensitive polymerizable layer. In FIG. 2, the sheet (22), the liquid (23), the photosensitive polymerizable layer (24) and the support (25) are heated in this order laminated on the hot plate (21).

The liquid used for heat development may be a liquid at the heat development temperature. That is, a substance having a melting point lower than the heat development temperature and a boiling point higher than the heat development temperature can be used. However, in operation, it is preferable to use a substance having a melting point of less than 20 ° C. (that is, a liquid at room temperature). Further, from the viewpoint of safety, it is preferable that the liquid is nonflammable or has a flash point of 150 ° C. or higher.

The liquid is preferably inert to the light-sensitive material. When the liquid used for heat development is a good solvent for the components in the photosensitive polymerizable layer, these components are dissolved in the liquid during development, which causes a problem in image formation. For this reason,
It is preferable to select and use a substance which is a poor solvent for the components in the photosensitive polymerizable layer. In particular, water is not preferable because it is a good solvent for the components in the photosensitive polymerizable layer. Also,
Water is not preferable also because the development temperature of 100 ° C. or higher is preferable.

However, the liquid is preferably hydrophilic and miscible with water. This is because, as described later, when heat-developed and immersed in an aqueous liquid (washing bath or etching liquid), a liquid miscible with water can be easily removed from the surface of the photosensitive material, and these processing liquids can be removed. This is because it does not get dirty. The liquid preferably forms a film on the photosensitive polymerizable layer as shown in FIGS. 1 and 2. In order to form a film, it is necessary to adjust the type and amount of the liquid so that all of the applied liquid is not absorbed by the photosensitive polymerizable layer. The thickness of the liquid film is preferably 0.1 μm or more, more preferably 0.5 μm or more.

Examples of preferred liquids include vegetable oils (eg,
Rapeseed oil, soybean oil, sesame oil), silicone oil (including those substituted with alkyl or aryl groups), isoparaffinic solvent (eg Exxon's "Isoper" group), hydrocarbon (eg kerosene, gas oil, liquid) Paraffin), salt fluorinated hydrocarbon, phthalic acid alkyl ester (eg, dibutyl phthalate, dioctyl phthalate), phosphoric acid ester (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), Citrate ester (eg, acetyl citrate tributyl), benzoate ester (eg, octyl benzoate), aliphatic ester (eg, dibutoxyethyl succinate, diethyl azelate) and trimesic acid ester (eg, tributyl trimesate), Polyethylene glycol, polypro Mention may be made of glycol).

Various known means may be used to apply the liquid onto the photosensitive polymerizable layer. Also, the liquid may be sprayed onto the photosensitive polymerizable layer. further,
Overlay another sheet containing liquid on top of the photopolymerizable layer,
The liquid may be transferred onto the photosensitive polymerizable layer. Of course, the method of using a sheet containing these sprays or liquids is also included in the "application" of the present invention.

A plastic film can be used as the sheet for covering the photosensitive polymerizable layer. A plastic film made of a polymer having a low oxygen permeability coefficient may be used. For polymers having a low oxygen permeability coefficient, JP-A-62-210447 and JP-A-62-210 are known.
It is described in each publication of No. 461. Sheet thickness is 10μ
The thickness is preferably in the range of m to 3 mm, more preferably in the range of 50 μm to 1 mm.

The thermal development can be carried out by bringing the photosensitive material into close contact with a heated object such as the hot plate shown in FIGS. The photosensitive material may be heated by irradiating it with infrared rays or high-frequency radio waves. Further, the photosensitive material may be brought into contact with heated gas.

The temperature of heat development is 60 ° C. or higher, but 10
It is preferably in the range of 0 to 200 ° C. The development time is preferably in the range of 1 to 180 seconds, more preferably 5 to 60 seconds.

[Layer Constitution of Photosensitive Material] The layer constitution of the photosensitive material of the present invention may be a single layer structure in which all necessary components are contained in one layer. Polymerizable photosensitive layer, overcoat layer,
A multi-layer structure including an image formation promoting layer and the like may be used. Japanese Patent Application 2
-295834 and 2-326260, a polymerizable photosensitive layer having a multi-layered structure in which a polymerizable layer containing a polymerizable compound and a photosensitive layer containing silver halide are separated. preferable. The order of laminating these layers varies depending on the purpose of use, but when used in a printing plate, for example, it is preferable that a polymerizable layer, a photosensitive layer, and an image formation promoting layer are provided in this order on a support. A photosensitive material having a multi-layer structure, in which the uppermost layer (surface layer) is covered with a polymer (eg, polyvinyl alcohol) which is substantially insoluble in a solvent other than water (eg, polyvinyl alcohol), is a photosensitive material during thermal development. Is not dissolved in the liquid for heat development, and is preferably used in the present invention.

The polymerizable layer is cured by the polymerization and / or crosslinking of the polymerizable monomer and / or the crosslinkable polymer caused by radicals (or other active species). The polymerizable layer is composed of a polymerizable compound and a binder polymer (a colorant if necessary). The thickness of the polymerizable layer can be determined according to the application. However, if it is too thin, the strength of the obtained image will be low, and if it is too thick, it will be difficult to cure it to the bottom of the layer. Preferably 0.1-
The thickness is 20 μm, more preferably 0.3 to 7 μm, still more preferably 0.5 to 3 μm. The coating amount of the polymerizable compound is 0.03 to ² g / m ² , more preferably 0.1 to ² g / m ² .
It is in the range of 1.0 g / m ² . Further, the coating amount of the binder polymer is in the range of 0.1 to 7 g / m ² , more preferably 0.3 to 3 g / m ² .

The photosensitive layer contains silver halide and generates radicals by imagewise exposure and thermal development. The generated radicals diffuse and enter the polymerizable layer to cure the polymerizable layer. The photosensitive layer preferably further contains a hydrophilic binder polymer. The layer thickness of the photosensitive layer is preferably in the range of 0.1 to 20 μm, more preferably 0.5 to 10 μm.

If desired, an overcoat layer or an image formation promoting layer can be further provided on the photosensitive layer. These layers typically include hydrophilic polymers. However, it is also possible to use hydrophobic polymers. For example, a hydrophobic polymer can be dissolved in a solvent and applied, or a polymer latex can be applied. In this case, these layers are peeled and removed after thermal development and prior to etching. The overcoat layer protects the light-sensitive material and prevents the ingress of oxygen in the air to enhance the degree of curing of the polymerizable layer. The image formation promoting layer is a layer in which the above-mentioned overcoat layer contains a component that promotes image formation (eg, a base or a base precursor, a reducing agent). Also works as. These layers can contain a matting agent. The matting agent reduces the tackiness of the layer surface and prevents adhesion when the light-sensitive materials are stacked. The layer thickness of these layers is 0.3 to 20 μm, more preferably 0.5 to
It is in the range of 10 μm.

Between each layer or between the support and the coating layer,
An intermediate layer can be provided. The intermediate layer functions as, for example, an antihalation layer containing a colorant, and a barrier layer that prevents components from moving between layers and diffusing or mixing during storage of the light-sensitive material. The material of the intermediate layer can be determined according to the application. For example, a hydrophilic polymer used for the photosensitive layer or the overcoat layer can be used. The layer thickness of the intermediate layer is preferably about 10 μm or less.

[Support] As the material of the support used in the present invention, paper, synthetic paper, paper laminated with synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide) , Nylon, cellulose triacetate), metal plates (eg, aluminum, aluminum alloys, zinc, iron, copper), and papers and plastic films laminated or vapor-deposited with these metals.

When the light-sensitive material of the present invention is used for a lithographic printing plate, the material for the support is preferably an aluminum plate, polyethylene terephthalate film, polycarbonate film, paper or synthetic paper. In addition, Japanese Examined Japanese Patent Publication Sho 48-1832
A composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film as described in Japanese Patent No. 7 is also preferable. The paper support is described in JP-A-61-3797 and JP-A-61-112150.

As a typical example, the case where an aluminum plate is used as a support will be described below. The support is subjected to surface treatment such as surface roughening treatment (graining treatment) or surface hydrophilization treatment, if necessary.

The surface roughening treatment (graining treatment) is an electrochemical graining method (eg, a method of making a grain in an aluminum plate by passing an electric current in a hydrochloric acid or nitric acid electrolyte solution). And / or mechanical graining method (eg, wire brush grain method of scratching aluminum surface with metal wire, ball grain method of graining aluminum surface with abrasive ball and abrasive, nylon brush and abrasive agent) Brush grain method of making a grain on the surface).

Next, the grained aluminum plate is chemically etched with acid or alkali. An industrially advantageous method is etching using an alkali. Examples of alkaline agents used include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of this alkaline solution is preferably in the range of 1 to 50% by weight, and the temperature of the alkaline treatment is preferably in the range of 20 to 100 ° C. Furthermore, it is preferable to adjust the conditions so that the dissolved amount of aluminum is 5 to 20 g / m ² .

Usually, after alkaline etching, the aluminum plate is washed with an acid to remove stains (smuts) left on the surface. Preferred acids used at this time are nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid.

The smut removing treatment after the electrochemical graining treatment is carried out by contacting with sulfuric acid at a concentration of 15 to 65% by weight at 50 to 90 ° C. as described in JP-A-53-12739, or It can be effectively carried out by the method described in JP-B-48-28123.

The aluminum plate surface-roughened as described above may be subjected to anodizing treatment or chemical conversion treatment, if necessary. The anodizing treatment can be performed by a known method. Specifically, in a solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc., an anodized film is formed on the aluminum surface by applying a direct current or an alternating current to the aluminum plate. .. The conditions of anodization vary depending on the electrolytic solution used. Generally, the concentration of the electrolytic solution is 1 to 80% by weight, the temperature of the electrolytic solution is 5 to 70 ° C., the current density is 0.5 to 60 amps / dm ² , and the voltage is 1 to 100.
v, the electrolysis time is preferably in the range of 10 to 100 seconds.

A particularly preferred anodizing method is a method of anodizing in sulfuric acid at a high current density (UK Patent No. 1412768).
And a method of anodizing phosphoric acid as an electrolytic bath (described in US Pat. No. 2,511,661).
Is.

The anodized aluminum plate may be treated with an alkali metal silicate (for example, the aluminum plate is immersed in an aqueous solution of sodium silicate) (as described in US Pat. Nos. 2,714,066 and 3,181,461), or A subbing layer may be provided on the surface of the support to improve the adhesion and printing properties of the aluminum support and the polymerizable layer.

The components constituting the undercoat layer include casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride resin, polyacrylic acid, monoethanolamine, diethanolamine, triethanolamine, tripropanolamine and their hydrochloric acid. Salts, oxalates, phosphates, aminoacetic acid, monoaminomonocarboxylic acids such as alanine, serine, threonine, oxyamino acids such as dihydroxyethylglycine, sulfur-containing amino acids such as cysteine and cystine, aspartic acid, glutamic acid, etc. Monoaminodicarboxylic acids, diaminomonocarboxylic acids such as lysine, amino acids having an aromatic nucleus such as p-hydroxyphenylglycine, phenylalanine and anthranil, sulfamic acid, cyclohexylsulfamim Aliphatic amino sulfonic acids such as acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyl iminodiacetic acid, hydroxyethyl ethylenediamine acetate, ethylenediamine diacetic acid,
(Poly) aminopolyacetic acid such as cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, etc. and some or all of the acid groups of these compounds are converted to salts such as sodium salt, potassium salt, ammonium salt, etc. Can be mentioned. These may be used in combination of two or more.

[Silver Halide] The silver halide in the present invention includes silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and the like. If it is a silver halide consisting of chlorine, bromine, and iodide,
Any particles can be used. The shape of silver halide grains is not limited to those having a regular crystal shape such as cube, octahedron and tetradecahedron, but those having anomalous crystal shape such as sphere and plate, twin plane It may have a crystal defect such as, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.01 micron or less, or large grains having a projected area diameter of up to about 10 microns. Also for polydisperse emulsions, US Pat.
No. 8, 3655394 and British Patent No. 14137.
The monodisperse emulsion described in each specification of No. 48 may be used, but an emulsion having high monodispersity is preferable. Also, tabular grains having an aspect ratio of about 5 or more can be used. Tabular grains are described in "Photographic Science and Engineering" by Gutoff.
and Engineering) ", Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 44.
Nos. 14310, 4433048 and 4439520
It can be easily adjusted by the method described in U.S. Pat. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide.

The silver halide grains include copper, thallium,
Lead, bismuth, cadmium, zinc, chalcogen (eg, sulfur, selenium, tellurium), gold or a Group VIII noble metal (eg, rhodium, iridium, iron, platinum, palladium) in the form of their respective salts according to the usual method. It can be added by adding during or after grain formation.
The specific method is described in US Pat.
No. 951933, No. 2448060, No. 2628.
No. 167, No. 2950972, No. 3488709.
No. 3,373,313, No. 3772031, No. 4,269,927, and Research Disclosure (RD), Vol. 134, No. 13452
(June 1975).

When an image is formed by high-intensity short-time exposure, iridium ions are added in an amount of 10 per mol of silver halide.
^-8 to 10 ^-3 mol is preferably used and 10 ^-7 to 10 ^-5
It is more preferable to use mol.

Two or more kinds of silver halide grains having different halogen compositions, crystal habits and grain sizes may be used in combination.

The silver halide is preferably used in the form of emulsion. The silver halide emulsion is described in Research Disclosure (RD) No. 17643 (December 1978)
Mon., pp. 22-23, "I. Emulsion prepa
ration and types) ", and No. 18716 (19)
(November 1979), p.648. The silver halide emulsion may be a negative type silver halide or an inversion type silver halide capable of directly obtaining a positive image. Silver halide emulsion,
Usually, chemical sensitization is performed after physical ripening, but chemical sensitization may not be performed. However, it is preferred to use relatively low fog silver halide grains. A light-sensitive material using such a silver halide grain is described in JP-A-63 / 1988.
-68830 gazette. Additives used in such processes are Research Disclosure, N.
o. 17643 and ibid. 18716. No. for chemical sensitizers. 17643 (page 23)
And No. No. 18716 (page 648, right column), for spectral sensitizers, see No. 17643 (pages 23-24) and N
o. No. 18716 (page 648, right column) about the supersensitizer. 18716 (page 649, right column-). Known additives other than the above are also described in the above two Research Disclosure magazines. For example, regarding the sensitivity increasing agent, No. 1871
No. 6 (page 648, right column) for the antifoggant and the stabilizer. 17643 (pages 24-25) and No. 1
8716 (page 649, right column-). As the silver halide, it is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in JP-A-63-68830. The silver halide emulsion may be a negative type silver halide or an inversion type silver halide capable of directly obtaining a positive image.

[Organic Metal Salt] An organic metal salt can be added to the photosensitive layer of the light-sensitive material of the present invention together with silver halide. As such an organic metal salt, it is particularly preferable to use an organic silver salt. Organic compounds used to form organic silver salts include US Pat.
Examples thereof include benzotriazoles, fatty acids and other compounds described in No. 26, columns 52 to 53. Further, silver salts of carboxylic acids having an alkyl group such as silver phenylpropiolic acid described in JP-A-60-113235 and JP-A-61-249044 and 64-64
The acetylene silver described in JP-A-57256 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0 to 10 mol, preferably 0 to 1 mol, per mol of silver halide. Further, instead of the organic silver salt, an organic compound constituting the organic silver salt is added to the photosensitive layer,
It may be partially reacted with silver halide in the photosensitive layer to be converted into an organic silver salt.

[Reducing Agent] The reducing agent used in the present invention has a function of reducing silver halide or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols,
2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones, 4
-Sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles,
Examples include α-sulfonamidoketones and hydrazines.
The above reducing agents are disclosed in JP-A-61-183640 and JP-A-61-183640.
-188535, 61-228441, 62-
70836, 62-86354, 62-863.
55, 62-206540, 62-26404.
No. 1, No. 62-109437, No. 63-254442.
No. 2, JP-A-1-267536, and No. 2-141756.
No. 2-141757, No. 2-207254, No. 2-262662, and No. 2-269352 (including those described as developers or hydrazine derivatives). For reducing agents, see T. James
4th "The Theory of the Photographic Process"
Pp. 291-334 (1977), Research Disclosure, Vol. 170, No. 17029, 9-.
Page 15, (June 1978), and ibid, Vol.17.
6, 17643, 22-31, (December 1978.
Month) Further, as in the light-sensitive material described in JP-A No. 62-210446, a reducing agent precursor that releases the reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. Among these reducing agents, those which have a basicity to form a salt with an acid can also be used in the form of a salt with an appropriate acid. These reducing agents may be used alone, or as described in each of the above publications, two or more reducing agents may be mixed and used. When two or more reducing agents are used in combination, the reducing agent interactions include firstly promoting reduction of silver halide (and / or organic silver salt) by so-called superadditivity, Cause the polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent in which the oxidant of the first reducing agent generated by reduction of silver halide (and / or organic silver salt) coexists (Or suppressing the polymerization) may be considered. However, in actual use, it is difficult to specify which of the above actions because the above reactions can occur simultaneously. The reducing agent is 0.1 to 10 per mol of silver halide.
It is used in a molar range, more preferably in a range of 0.5 to 5 mol. Specific examples of the reducing agent are shown below.

[0044]

[Chemical 1]

[0045]

[Chemical 2]

[0046]

[Chemical 3]

[0047]

[Chemical 4]

[0048]

[Chemical 5]

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

[Chemical 8]

[0052]

[Chemical 9]

[0053]

[Chemical 10]

[0054]

[Chemical 11]

[0055]

[Chemical 12]

By adjusting the kind and amount of the above reducing agent, the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image is not formed is selectively polymerized. be able to. The reducing agent develops silver halide and is itself oxidized to an oxidant. When the oxidant of this reducing agent decomposes in the layer to generate radicals,
Polymerization occurs in the portion where the latent image of silver halide is formed. Examples of such reducing agents include hydrazines. On the other hand, when the oxidant does not generate (or does not easily generate radicals) and the reducing agent itself or the oxidant has a polymerization inhibiting action (examples of such reducing agents include 1-phenyl-3-pyrazolidones and Hydroquinones can be mentioned) and a part where a latent image of silver halide is not formed by including a polymerization initiator (radical generator) together with a reducing agent (the oxidant is more prohibited than the reducing agent in the polymerization). Polymerization occurs in the case where the action is strong) or in the portion where the latent image is formed (when the reducing agent has a stronger polymerization inhibiting action than the oxidant). In this case, it is necessary to add a polymerization initiator, which is decomposed by heating or light irradiation and uniformly generates radicals, to the photosensitive material as described below. Regarding such an image forming method and a reducing agent used, JP-A-61-75342 is used.
No. 61-243449, No. 62-70836,
62-81635, 63-316038, JP-A-2-141756, 2-141757, 2-.
207254 and 2-262662, and U.S. Pat. No. 4,690,098 and EP Patent 0202.
No. 490 is described in each specification.

[Polymerization Initiator] Examples of the thermal polymerization initiator include those described in “Additional Polymerization / Ring-Opening Polymerization” (1983, Kyoritsu Shuppan), edited by The Society of Polymer Science and the Society for Polymer Experimental Studies, and pages 6-18. It is described in, for example, JP-A-61-243449. Examples of the thermal polymerization initiator include azo compounds (eg, azobis (isobutyronitrile) and 1,1′-azobis (1-cyclohexanecarbonitrile)), peroxides (eg, benzoyl peroxide and potassium persulfate). ) Can be mentioned. The photopolymerization initiator is, for example, 125 in "Chemical Review", Volume 68 (1968) by Oster et al.
~ 151 pages and "Light-Sensitive System" by Kosar
(John Wiley & Sons, 1965) pp. 158-193, JP-A-61-75342, JP-A-2-20.
No. 7,254, carbonyl compounds (eg, α-alkoxyphenyl ketones, polycyclic quinones, benzophenone derivatives, xanthones, thioxanthones, benzoins, commercially available photoinitiators (eg, Ciba Geigy) "Irgacure 651" and "Irgacure 907")), halogen-containing compounds, redox couples of photoreducible dyes and reducing agents, organic sulfur compounds,
Peroxides, optical semiconductors, metal compounds, etc. are used.

The polymerization initiator is used per 1 g of the polymerizable compound,
It is preferably used in the range of 0.001 to 0.5 g,
More preferably, it is used in the range of 0.01 to 0.2 g.

[Polymerizable Compound] As the polymerizable compound in the present invention, a polymerizable monomer or a crosslinkable polymer can be used. The polymerizable monomer and the crosslinkable polymer may be used in combination. Examples of the polymerizable monomer include compounds having addition polymerization or ring-opening polymerization. The compound having an addition polymerizable property includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable property includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable. Examples of the compound having an ethylenically unsaturated group include acrylic acid and salts thereof, acrylic acid esters, acrylamides,
Methacrylic acid and its salts, methacrylic acid esters,
Methacrylicamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and their derivatives are listed. it can. Acrylic acid esters or methacrylic acid esters are preferred. Specific examples of acrylic acid esters include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethyl acrylate, dicyclohexyloxyethyl acrylate, tricyclodecanyloxy acrylate, nonylphenyloxyethyl. Acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, trimethylolpropane triacrylate, tricyclodecane dimethylol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylenated bisphenol A diacrylate,
Diacrylate of a condensate of 2,2-dimethyl-3-hydroxypropionaldehyde and trimethylolpropane, triacrylate of a condensate of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol, and polyoxyethylenated bisphenol F Diacrylate, polyurethane acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,
3-dioxane diacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5,5-dihydroxymethyl-1,3-dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, hydroxypoly Mention may be made of ether polyacrylates, polyester acrylates and polyurethane acrylates. Specific examples of the methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate and polymethacrylate. Examples thereof include compounds in which a part or all of the acryloyl group of the polymerizable monomer compound described as a specific example of the above-mentioned acrylic acid esters such as dimethacrylate of oxyalkylenated bisphenol A is replaced with a methacryloyl group. The polymerizable monomer can also be selected from commercially available products and used. Examples of commercially available polymerizable monomers include Aronix M-309, M-310, M-315, and M-40 manufactured by Toagosei Kagaku Kogyo Co., Ltd.
0, M-210, M-6100, M-8030 and M-8100, manufactured by Nippon Kayaku Co., Ltd., Kayarad TMP.
TA, DPHA, DPCA-60, HX-220, HX
-620, R-167, R-310, R-330, R-
551, R-604, R-684, R-712, manufactured by Shin Nakamura Chemical Co., Ltd., NK ester A-1000, A-60.
0, A-400, A-200, 14G, 23G, SARTOM
Examples include SARTOMER-454 and -9035 manufactured by ER Corporation.

As the crosslinkable polymer, any known polymer having a radical-reactive group can be used. These polymers may be homopolymers or copolymers with monomers that do not have groups reactive with radical species. Such a polymer is a polymer having (A) a radical (a polymerization initiation radical or a growth radical in the polymerization process of a polymerizable monomer) to which a double bond group can be added, in the main chain or side chain of the molecule, And (B) main chain or side chain atoms (hydrogen atom, halogen atom such as chlorine) due to radicals
Is a polymer that is easily extracted to generate a polymer radical. Examples of the polymer (A) include polymers having an ethylenically unsaturated double bond in the side chain as described in JP-A No. 64-17047 (eg,
Allyl (meth) acrylate polymers (including copolymers), 1,2-polybutadiene, 1,2-polyisoprene) and polymers having unsaturated double bonds in the main chain (eg, poly-1,4-butadiene, poly) Mention may be made of -1,4-isoprene (including copolymers), natural and synthetic rubbers. As an example of the above-mentioned polymer of (B), "polymer reaction" (edited by The Polymer Society of Japan / Kyoritsu Shuppan, 19
The polymers described on pages 147 to 192 of 1978) can be mentioned. Specifically, poly (meta)
Acrylate, polyvinyl butyrate, polyvinyl formal, polyvinyl pyrrolidone, polyvinyl acetate, polyvinylidene chloride, vinyl acetate-ethylene copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated polyethylene, chlorinated polypropylene, polycarbonate, diacetyl cellulose, cellulose acetate butyrate Rate, triacetyl cellulose, ethyl cellulose,
Polyvinyl pyridine and polyvinyl imidazole can be mentioned. As described later, when the etching treatment is performed with an alkaline aqueous solution after the polymerization, the crosslinkable polymer preferably has an acidic functional group in its molecule. Examples of acidic functional groups include carboxyl groups,
Examples thereof include acid anhydride groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups and sulfonimide groups. Specific examples thereof include homopolymers or copolymers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride. For copolymers,
The molar content of the monomer having an acidic group is in the range of 1 to 50%, more preferably 5 to 30%.

The above-mentioned polymerizable compounds may be used alone or in combination of two or more kinds. Regarding a light-sensitive material in which two or more kinds of polymerizable compounds are used in combination, JP-A-62-
It is described in Japanese Patent Publication No. 210445. The polymerizable compound is contained in the polymerized layer in an amount of preferably 3 to 90% by weight, more preferably 15 to 60% by weight, based on the total amount of the layer.

[Binder of Polymerizable Layer] A binder may be further added to the polymerizable layer of the photosensitive material of the present invention in order to improve the strength. As a binder,
Natural and synthetic polymeric compounds can be used. When a crosslinkable polymer is used as the polymerizable compound, the crosslinkable polymer functions not only as the polymerizable compound but also as the binder. Therefore, the crosslinkable polymers described above can be and are preferably used as binders. Specific examples of the binder include addition polymerization type synthetic homopolymers and copolymers (eg, homopolymers and copolymers of various vinyl monomers), polycondensation type synthetic homopolymers and copolymers (eg, polyester, polyamide, polyurethane, Polyester-polyamide). As will be described later, when the etching treatment is performed with an alkaline aqueous solution after the polymerization, the polymer used as the binder preferably has an acidic functional group in its molecule. Examples of the acidic functional group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, a sulfonic acid group,
Mention may be made of sulfonamide groups and sulfonimide groups. Specific examples thereof include homopolymers or copolymers of (meth) acrylic acid, styrene sulfonic acid or maleic anhydride. In the case of a copolymer, the molar content of the monomer having an acidic group is 1 to 50.
%, More preferably 5 to 30%. As the polymer used for the binder, a crosslinkable polymer having an acidic functional group in its molecule is particularly preferable.
An example of such a polymer is a copolymer of allyl (meth) acrylate and (meth) acrylic acid. As a binder or polymerizable compound,
When a polymer having an ethylenically unsaturated double bond in the side chain is used, an image can be obtained even if the polymerizable layer does not contain a polymerizable monomer, but in general, it is preferable to use the polymerizable monomer in combination. It is preferable because the hardness can be increased. Further, an image can be obtained even if the polymerizable layer does not contain a binder but contains only the polymerizable monomer, but when the polymerizable monomer is a liquid, the polymerizable layer becomes too soft, which is not preferable. The amount of the binder added to the polymerizable layer is not particularly limited as long as it does not interfere with the curing reaction of the polymerizable layer, but is 0 to 80% by weight, preferably 0 to 70% by weight based on the entire polymerizable layer.

[Hydrophilic Binder Polymer] As the binder used in the photosensitive layer, the overcoat layer or the image formation promoting layer of the photosensitive material of the present invention, any binder can be used as long as the characteristics of the photosensitive layer are not significantly impaired. However, it is preferable to use a hydrophilic binder. A hydrophilic binder is a hydrophilic group or // in the molecular structure.
And a binder having a bond. Examples of hydrophilic groups include carboxyl groups, alcoholic hydroxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfonimide groups and amide groups.
Examples of hydrophilic bonds include urethane bonds, ether bonds and amide bonds. It is preferable to use a water-soluble polymer and / or a water-swellable polymer as the hydrophilic binder polymer. The water-swellable polymer is a polymer that has an affinity for water but is not completely soluble in water because the binder itself has a crosslinked structure and the like. As the water-soluble or water-swellable binder, a natural or synthetic polymer compound can be used. Examples of natural polymers include water-soluble polysaccharides (eg, starch derivatives, cellulose derivatives, alginic acid, pectic acid, gum arabic, pullulan, dextran) and proteins (eg, casein, gelatin). These may be artificially modified if necessary. It can also be used after being modified or crosslinked during coating and drying. As the synthetic polymer, a polymer of a water-soluble monomer or a copolymer of this and another monomer can be used. As the water-soluble monomer in this case, a carboxyl group, an acid anhydride group, a hydroxyl group, a sulfonic acid (salt) group,
Examples thereof include monomers having a chemical structure such as an amide group, an amino group, and an ether group. Regarding such monomers, "Applications and Markets of Water-soluble Polymers" (CMC
See pages 16-18). A copolymer obtained by polymerizing these monomers or crosslinking a polymer obtained by copolymerizing with another monomer can also be used (for example, the copolymer described in US Pat. No. 4,913,998). As other synthetic polymers, polyvinyl alcohol, polyvinyl ether, polyvinylpyrrolidone, polyethylene oxide and derivatives or modified products thereof can be used. For example, in the case of polyvinyl alcohol, those having various degrees of saponification can be used. Further, copolymer modified polyvinyl alcohol can also be used. The copolymerization modification is a method in which a copolymer of vinyl acetate and another monomer is saponified to obtain modified polyvinyl alcohol. As the monomer to be copolymerized, any monomer can be used as long as it is copolymerized with vinyl acetate. Examples of copolymerizable monomers include ethylene, higher vinyl carboxylates, higher alkyl vinyl ethers, methyl methacrylate and acrylamide. Further, post-modified polyvinyl alcohol can also be used. The post-modification is a method of modifying by a polymer reaction with a compound having reactivity with the hydroxyl group of polyvinyl alcohol. Specifically, the hydroxyl group is modified by etherification, esterification, acetalization, or the like. Furthermore, it is also possible to use crosslinked polyvinyl alcohol. In this case, polyvinyl alcohol is cross-linked using an aldehyde, a methylol compound, an epoxy compound, a diisocyanate, a divinyl compound, a dicarboxylic acid or an inorganic cross-linking agent (eg boric acid, titanium, copper) as a cross-linking agent. These modified polyvinyl alcohols and cross-linked polyvinyl alcohols are illustrated in "Poval", Vol. 3, "Polymer Publishing" (pp. 281-285 and 256-260). The molecular weight of these hydrophilic polymers is preferably in the range of 3000 to 500,000. The coating amount is 0.05 to 20 g / m ² , more preferably 0.1 to 10 g / m ² .

In the method of the present invention, a liquid is applied on the photosensitive polymerizable layer and heat development is carried out with the photosensitive polymerizable layer covered with a sheet, so that oxygen in the air is completely shielded. Therefore, a polymer having low oxygen permeability may be used. For this purpose, it is preferable to use a polymer having a low oxygen permeability as the hydrophilic binder described above. Its oxygen permeability coefficient is 1.0 × 10 ^-11 cc ・ cm / cm ²・ s
It is preferably ec · cm · Hg or less. As the polymer having low oxygen permeability, a polyvinyl alcohol-based polymer,
Copolymers of gelatin and vinylidene chloride are preferred. Here, the polyvinyl alcohol polymer means polyvinyl alcohol and modified polyvinyl alcohol (for example, saponified block copolymer of polyvinyl acetate and another monomer). Molecular weight is about 3000
The range of 500,000 is preferable. As a polymer having low oxygen permeability, the saponification degree is 50% or more, more preferably 80%.
Above, more preferably 95% or more of polyvinyl alcohol is particularly preferable.

[Base or Base Precursor] The light-sensitive material used in the present invention may contain a base or a base precursor. As the base and the base precursor, inorganic bases and organic bases, or base precursors thereof (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used. Examples of inorganic bases include JP-A-62-20
It is described in Japanese Patent No. 9448. Examples of organic bases include
Tertiary amine compounds (described in JP-A-62-170954), bis or tris or tetraamidine compounds (described in JP-A-63-316760) and bis or tris or tetraguanidine compounds (JP-A-64-68746). (Described in Japanese Patent Publication). In the present invention, a base having a pKa of 7 or higher is preferred. In the present invention, a base precursor is preferable to a base from the viewpoint of storage stability of the light-sensitive material. Examples of preferable base precursors include salts of organic acids and bases that are decarboxylated by heating (JP-A-63-316760 and 64-6).
8746, 59-180537 and 61-3
13431) and urea compounds that release a base upon heating (described in JP-A-63-96159).
Can be mentioned. Further, as a method of releasing a base by utilizing a reaction, a reaction with a transition metal acetylide or a salt containing an anion having an affinity higher than that of the acetylide anion for the transition metal ion (described in JP-A-63-25208) Or a basic metal compound which is poorly soluble in water and a compound capable of undergoing a complex formation reaction with a metal ion constituting the basic metal compound in water as a medium, and between these two compounds in the presence of water. And a method of releasing a base by the reaction (described in JP-A-1-3282). The base precursor of the present invention includes 50 ° C to 20 ° C.
It preferably releases a base at 0 ° C.
It is more preferable that it releases a base at a temperature of from 160 ° C to 160 ° C. The light-sensitive material using a base or a base precursor is described in JP-A-62-264041. Further, for a light-sensitive material using a tertiary amine as a base, see JP-A-62-1170954, and for a light-sensitive material using a fine particle dispersion of a hydrophobic organic base compound having a melting point of 80 to 180 ° C. JP 62
JP-A-63-7 discloses a light-sensitive material using a guanidine derivative having a solubility of 0.1% or less.
No. 0845 discloses a light-sensitive material using a hydroxide or salt of an alkali metal or an alkaline earth metal, and each is described in JP-A-62-209448. Further, regarding a light-sensitive material using an acetylide compound as a base precursor, JP-A-63-24242 discloses that a propiolic acid salt is used as a base precursor.
Further, a light-sensitive material containing silver, copper, a silver compound or a copper compound as a catalyst for a base-forming reaction is disclosed in JP-A-63-46.
No. 446, the propiolate and the silver, copper,
Regarding a light-sensitive material containing a silver compound or a copper compound in a state of being isolated from each other, JP-A-63-81338 discloses that the propiolic acid salt and the silver, copper, the silver compound or the copper compound and the coordination in the free state. Japanese Patent Application Laid-Open No. 63-97942 discloses a light-sensitive material containing a child and a light-sensitive material containing a heat-fusible compound as a reaction accelerator for a base formation reaction in JP-A-63-97942. Japanese Patent Application Laid-Open No. 63-48453 discloses a light-sensitive material containing a sulfonylacetate as a base precursor and further containing a heat-meltable compound as a reaction accelerator for a base-forming reaction. Regarding a light-sensitive material using a compound to which an isocyanate or isothiocyanate is bound, see Japanese Patent The 63-96652 discloses further the light-sensitive material comprising a nucleophilic agent as a decomposition accelerator for this compound is described respectively in JP-A-63-173039. For a light-sensitive material using a bis or trisamidine salt of a decarboxylable carboxylic acid as a base precursor, see JP-A-64-9441, and for a light-sensitive material using a bis or trisguanidine salt, JP-A-64-941. Each of them is described in Japanese Patent Publication No. 68749. The base and the base precursor can be used in combination. The base or base precursor is preferably used in an amount of 0.5 to 50 mol, and more preferably 1 to 20 mol, per mol of silver halide. In the image forming method of the present invention, instead of adding a base or a base precursor to the light-sensitive material, a base may be added to the liquid for heat development described above.

[Heat Development Accelerator] As the heat development accelerator,
By heating, it melts more in the layer and dissolves various substances,
Compounds conventionally known as "hot solvents", for example, U.S. Pat. Nos. 3,347,675 and 3,667,959, Research Disclosure, December 1976, 26.
Page 28, JP-A-62-151841 and JP-A-62-1815.
1743, 62-183450, 63-243.
The heat-melting compounds such as polyethylene glycols, sulfonamides and cyclic amides described in JP-A Nos. 835 and 63-253934 are used. A compound having a plasticizing effect on the binder used in any layer of the light-sensitive material at room temperature or at the time of heating, for example, a known compound known as a plasticizer of a polymer compound can also be used as a thermal development accelerator. is there. As such a plasticizer,
"Plastic compounding agent" Taiseisha, P21-63; "Plastics Additives, 2nd edition"
2nd Edition) Hanser Publishers, Chap.5P251-296;
"Thermoplastic Additives" (Thermoplas
tics Additives) Marcel Dekker Inc. Chap. 9 P345-37
9; "Plastics Additives An Industri"
al Guide) Noyes Publications, Section-14 P333-485
"The Technology of Solvents and
The Plasticizers "(The Technology of Solvents
andPlasticizers) John Wiley & Sons Inc. Chap.15
P903-1027); "Industrial Plasticizers, Pergamon Pres"
s); "Plasticizer Technology Volume 1" (P
lasticizer Technology Vol.1, Reinhold Publishing C
orp.); “Plasticization and Pluiser Process”
The plasticizers described in sticizer Process, American Chemistry) can be used. Depending on the compound, it may be difficult to distinguish which of the above-mentioned two functions it has, and in some cases it may have both functions. Examples of particularly preferable thermal development accelerators include ureas (eg, urea, ethylene urea,
Methylurea, dimethylurea, ethylurea, propyleneurea), amides (eg, acetamide, propionamide), sulfamides, sulfonamides, polyhydric alcohols (eg, sorbitol, trimethylolethane,
Trimethylolpropane, pentaerythritol, glycerin, ethylene glycol, propylene glycol,
Polyethylene glycol, polypropylene glycol,
Butanediol, hexanediol), sugars, urea resins and phenolic resins can be mentioned. In addition, two or more of the above thermal development accelerators can be used in combination. It is also possible to add it by dividing it into two or more layers. In the image forming method of the present invention, instead of adding the heat development accelerator to the light-sensitive material, the heat development accelerator may be added to the above-mentioned liquid for heat development.

[Coloring Agent] In the present invention, a coloring agent may be added to the light-sensitive material for the purpose of preventing halation and irradiation or coloring the polymerized image. As the colorant for this purpose, any known colorant regardless of pigment or dye may be used, as long as it does not significantly hinder the polymerization and curing reaction of the polymerizable layer or does not significantly hinder the photosensitivity and developability of the silver halide. It is possible to use. When the colorant is used for the purpose of preventing halation or coloring the image, it is preferably added to the polymerizable layer. Also,
When used for the purpose of preventing irradiation, it is preferably added to the photosensitive layer. When a coloring agent is added to prevent halation and irradiation, it is preferable that the coloring agent can absorb light in the photosensitive wavelength region of silver halide. Examples of the pigment that can be used as the colorant include commercially available pigments and Color Index (CI) Handbooks,
The pigments described in "Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" (CMC Publishing, 1984) are used. it can. Examples of the types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded dyes. Specifically, carbon black, insoluble azo pigment,
Azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyed lake pigments, Azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments and the like can be used. These pigments may be used without surface treatment or may be subjected to surface treatment before use. The surface treatment method includes a method of surface coating resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface. Conceivable. The above-mentioned surface treatment methods are described in "Properties and Applications of Metal Soap" (Koshobo), "Printing Ink Technology" (CMC Publishing, 1
984) and "Latest Pigment Application Technology" (CMC Publishing, 1986). The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm,
It is more preferably in the range of 0.05 μm to 1 μm. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill and a pressure kneader.
For details, see "Latest Pigment Application Technology" (CMC Publishing, 1986).
Annual publication). As the dye that can be used as the colorant, commercially available dyes and known dyes described in the literature (for example, “Handbook of Dyes” edited by the Society of Organic Synthetic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes,
Examples include dyes such as quinone imine dyes and methine dyes. Dyes for preventing irradiation, which have little effect on the sensitivity of silver halide, are disclosed in JP-B-41-20389 and JP-A-4-20389.
No. 3-3504, No. 43-13168, and Japanese Patent Laid-Open No. Hei 2
-39042 and U.S. Pat. No. 369703.
No. 7, No. 3423207, No. 2865752,
British Patent Nos. 1030392 and 1100546
The items described in each specification can be cited as examples. The content of the colorant is not particularly limited as long as it does not significantly hinder the polymerization reaction of the polymerizable layer or the light sensitivity and developability of the silver halide. Also,
The appropriate amount of addition varies depending on which layer contains the pigment and whether the pigment or dye is used. In addition, it is difficult to unconditionally specify the optimum addition amount because the appropriate addition amount changes depending on the absorbance of the colorant, but 0.01 to 2 g
/ M ² , more preferably 0.05 to 1 g / m ² .

[Antifoggant, Development Accelerator, Stabilizer] In order to improve photographic characteristics, an additive such as an antifoggant, a silver development accelerator that accelerates the development of silver halide, or a stabilizer is added. It may be contained in the layer. Examples of those are:
Research Disclosure No. 17643, 2
Azoles and azaindenes described on pages 4 to 25 (1978), nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, and acetylene compounds described in JP-A-62-87957. Can be mentioned. The amount of these compounds used is in the range of 10 ^-7 to 1 mol per mol of silver halide.

[Development Stopping Agent] In the present invention, various development stopping agents may be used for the purpose of always obtaining a constant image with respect to the processing temperature and the processing time during the heat development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the layer to stop the development after proper development, or to inhibit development by interacting with silver or a silver salt. It is a compound that causes. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For the development stopper, see JP-A-62-25315.
No. 9, JP-A-2-42447 and JP-A-2-262.
It is described in each publication of No. 661. The development terminator may be added to any layer.

[Surfactant] In the present invention, a surfactant can be added to any layer. Known surfactants can be used as the surfactant. Examples include nonionic activators, anionic activators, cationic activators, fluorine-containing activators, and surfactants described in JP-A-2-195356. In particular, sorbitans, polyoxyethylenes, and fluorine-containing surfactants are preferable.

[Matting Agent] Examples of the matting agent that can be contained in the overcoat layer or the image formation promoting layer provided on the uppermost layer of the light-sensitive material are various polymer powders (eg, natural products such as starch, polyethylene, etc.). And other synthetic polymers). The particle size is preferably in the range of about 1 to 50 μm.

[Polymerization Inhibitor] A polymerization inhibitor may be added to the polymerizable layer in order to prevent the polymerizable compound from polymerizing during storage of the light-sensitive material. As the polymerization inhibitor for this purpose, any conventionally known polymerization inhibitor can be used. Examples of the polymerization inhibitor include nitrosamine compounds, thiourea compounds, thioamide compounds, urea compounds, phenol derivatives, nitrobenzene derivatives and amine compounds. More specifically, cuperone aluminum salt, N-nitrosodiphenylamine, allylthiourea, arylphosphite, p
-Toluidine, φ-tortinone, nitrobenzene, pyridine, phenathiazine, β-naphthol, naphthylamine, t-butylcatechol, phenothiazine, chloranil, p-methoxyphenol, pyrogallol, hydroquinone, and alkyl- or aryl-substituted hydroquinone.

[Image Forming Method] Image formation by thermal development is performed as follows. That is, when a latent image is formed on a photosensitive layer containing silver halide by imagewise exposure, and then (or simultaneously) the photosensitive layer is uniformly heated (heat-developed) to develop the silver halide on which the latent image is formed. At the same time, the polymerizable compound in that portion (or in the portion where the latent image is not formed) is polymerized and cured to form a polymerized image. Image exposure is performed using a light source that emits light having a wavelength corresponding to the spectral sensitivity (sensitizing dye) of silver halide. Examples of light sources that can be used include tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps,
Examples thereof include mercury lamps, lamps such as carbon arc lamps, various lasers (eg, semiconductor lasers, helium neon lasers, argon ion lasers, helm cadmium lasers), light emitting diodes, cathode ray tubes, and the like. The exposure wavelength is generally visible light, near-ultraviolet light, or near-infrared light, but X-rays or electron beams may be used. The exposure amount is determined by the sensitivity of silver halide, but is generally 0.01 to
10,000 ergs / cm ² , more preferably 0.1
It is in the range of 1000 erg / cm ² . When the support is transparent, it can be exposed through the support from the back side of the support. The heat development of the present invention is as described above. When a polymerization image is formed by utilizing the polymerization inhibiting action of the reducing agent or its oxidant, it is necessary to uniformly generate radicals from the polymerization initiator. When a thermal polymerization initiator is used, heating can be performed only once, because radicals can be generated by heating during thermal development. When a photopolymerization initiator is used, it is necessary to expose the entire surface after thermal development in order to generate radicals. The light at this time must have a wavelength absorbed by the photopolymerization initiator. The light source can be appropriately selected from those exemplified as the light source used for the image exposure. The exposure amount is about 10 ³
It is in the range of 10 ⁷ ergs / cm ² .

After thermal development, the obtained polymerized image has a chemical property and a physical property (for example, solubility, surface tackiness, adhesion strength with a support, softening) between the hardened portion and the uncured portion. The post-treatment is carried out by utilizing the difference in points, refractivity, dielectric constant, diffusivity, and colorability. In the method of the present invention, after thermal development, the sheet covering the photosensitive polymerizable layer is peeled from the photosensitive material, and then post-treatment is carried out. Examples of the post-processing include the following processing. 1. By utilizing the difference in solubility between the uncured portion and the cured portion, only the uncured portion is eluted to form a polymer image. 2. The uncured portion or the cured portion is selectively transferred to another sheet by utilizing the difference in adhesion strength between the uncured portion and the support of the cured portion. 3. By utilizing the difference in surface tackiness between the uncured portion and the cured portion, a coloring substance (toner) is attached to the uncured portion to visualize the image. 4. The image is visualized by selectively dyeing the uncured portion or the cured portion. Also, these can be used in combination. For these image forming methods, see Japanese Patent Application No. 32-32626.
No. 0, No. 3-131788, No. 3-131789,
It is described in the specifications of No. 3-131790 and No. 3-131791.

The image thus obtained can be used for printing plates, color proofs, hard copies, reliefs and the like. When the uncured portion is eluted to form a polymer image, after the thermal development, it is immersed in a liquid (etching solution) capable of removing the uncured portion of the polymerizable layer. For the etching liquid,
A liquid that dissolves or swells the uncured polymerizable layer, such as an organic solvent, an alkaline aqueous solution or a mixture thereof, is used.
As the alkaline compound, potassium hydroxide, sodium hydroxide, potassium silicate, sodium silicate, potassium metasilicate, sodium metasilicate, potassium phosphate, sodium phosphate, ammonia, and monoethanolamine, diethanolamine, triethanolamine, etc. The amino alcohols can be mentioned. Various organic solvents may be added to the water-based etching solution, if necessary. Examples of the organic solvent include lower alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol, and phenethyl alcohol, aromatic alcohols, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cellosolves, and the amino alcohols described above as bases. Etc. Further, a surfactant, a defoaming agent, and other additives can be added to the etching solution as needed. Further, a commercially available developing solution for a printing plate can also be used. The light-sensitive material that has undergone the heat development may be directly immersed in an etching solution, or may be previously immersed in an etching solution after washing or peeling off a photosensitive layer other than the polymerizable layer to remove it. ..

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these.

[0077]

【Example】

[Example 1] "Preparation of aluminum support" A surface of an aluminum plate having a thickness of 0.30 mm was covered with a nylon brush and a pumice stone (4
(00 mesh) in water, and after graining, it was thoroughly washed with water. Next, it was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, and then washed with running water. It was neutralized and washed with a 20% aqueous nitric acid solution, and then washed with water. The obtained aluminum plate was subjected to a sinusoidal alternating waveform current (conditions: voltage at anode 12.7 v, ratio of electricity at cathode to electricity at anode was 0.8, electricity at anode was 160 coulomb / dm ² ). Then, electrolytic graining treatment was performed in a 1% nitric acid aqueous solution. The surface roughness of the obtained plate was 0.6 μm (Ra indication). Following this treatment, it was desmutted in a 30% aqueous sulfuric acid solution at 55 ° C. for 2 minutes. Next, ² so that the thickness becomes 2.7 g / dm 2.
Anodizing was performed in 0% sulfuric acid aqueous solution (current density 2
A / dm ² ). The obtained aluminum plate was immersed in a 3 wt% sodium silicate aqueous solution at 70 ° C. for 20 seconds, washed with water and dried.

[Formation of Polymerizable Layer] The following coating liquid was applied onto the support and dried to form a polymerizable layer having a thickness of about 1.3 μm.

──────────────────────────────────── Coating solution for the polymerizable layer ───── ─────────────────────────────── Dipentaerythritol hexaacrylate 2.5g Allyl methacrylate / methacrylic acid copolymer (copolymerization Ratio = 83/17) 20% by weight propylene glycol monomethyl ether solution 37.5 g The following reducing agent 2.0 g The following pigment dispersion 13.0 g Methyl ethyl ketone 74.0 g ────────────── ───────────────────────

[0080]

[Chemical 13]

──────────────────────────────────── Pigment dispersion ──────── ──────────────────────────── Chromophtal red A2B 18g Benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 12g Cyclohexanone 30g Propylene glycol monomethyl ether 40g ─────────────────────────────────────

[Formation of Photosensitive Layer] (Preparation of Silver Halide Emulsion) A suitable amount of aqueous ammonia was added to a container containing gelatin, potassium bromide and water and heated to 55 ° C. While maintaining the pAg value of 7.60, the aqueous solution of silver nitrate and an aqueous solution of potassium bromide to which hexachloroiridium (III) is added so that the molar ratio of iridium to silver is 5 × 10 ^-7 mol are double-jet. Method, and then potassium iodide was added to prepare monodisperse silver iodobromide emulsion grains having an average grain size of 0.25 μm (silver iodide content: 2 mol%). In these emulsion grains, 98% of the total number of grains were present within ± 40% of the average grain size. After the emulsion was desalted, the pH was adjusted to 6.2 and the pAg was adjusted to 8.6, and then gold / sulfur sensitization was performed with sodium thiosulfate and chloroauric acid, and then the following spectral sensitizing dye (Dye -1) 2 mol / 1 methanol was added at 200 cc / kg of emulsion, and the mixture was added at 60 ° C. for 15
A silver halide emulsion was prepared by stirring and holding for a minute.

[0083]

[Chemical 14]

[Formation of Photosensitive Layer] A coating solution having the following components was prepared, coated on the polymerizable layer and dried to form a photosensitive layer having a dry film thickness of about 1.2 μm.

──────────────────────────────────── Coating solution for the photosensitive layer ───── ─────────────────────────────── Polyvinyl alcohol with a saponification degree of 79.5% (trade name: PVA-420, Kuraray Co., Ltd.) 10% by weight aqueous solution 10.5 g 0.11% by weight methanol solution of the following additive (A-1) 0.83 g The above silver halide emulsion 0.5 g The following surfactant (SA- 1) 5% by weight aqueous solution 0.4 g water 7.8 g ─────────────────────────────────────

[0086]

[Chemical 15]

[0087]

[Chemical 16]

[Preparation of Base Precursor Dispersion] 250 g of powder of the following base precursor (BP-1) was used in a Dynomill disperser and 750 g of a 3% by weight aqueous solution of polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.). Dispersed in. The particle size of the base precursor is about 0.5
It was less than μm.

[0089]

[Chemical 17]

[Formation of image formation promoting layer] (Formation of image forming promoting layer) Next, a liquid having the following composition was mixed to prepare a coating liquid. This was applied onto the photosensitive layer and dried to form an image formation promoting layer having a dry film thickness of about 3.3 μm.

──────────────────────────────────── Coating solution for the image formation promoting layer ──── ──────────────────────────────── Polyvinyl alcohol with a saponification degree of 98.5% (trade name: PVA-110, Kuraray 100.0% by weight aqueous solution 20.0 g of the above base precursor (BP-1) dispersion 1.25 g 5% by weight aqueous solution of the above surfactant (SA-1) 4.0 g ───── ───────────────────────────────

(Image formation) The sample prepared as described above was brought into close contact with the original film and exposed for 1 second through a band filter which passed a light of 500 nm using a 500 W tungsten lamp. Next, a liquid paraffin layer having a thickness of about 1 mm was applied on the surface of the light-sensitive material. Further, the surface thereof was covered with a polyethylene terephthalate film having a thickness of 100 μm. When the back surface (aluminum support side) of the light-sensitive material was brought into close contact with a hot plate heated to 135 ° C. and heat development was carried out for 20 seconds, a silver image was observed in the exposed portion. Since the surface of the photosensitive material was covered with a sheet, the above operation could be easily performed. Next, peel off the sheet from the photosensitive material, and use Fuji PS Developer D.
After immersion in N-3C (manufactured by Fuji Photo Film Co., Ltd.) at room temperature for 1 minute to perform etching and then washing with water, the unexposed portion of the polymerized layer was eluted and removed, and the exposed portion of the polymer was colored red. An image was formed. The printing plate thus obtained was mounted on a Heidel KOR-D printing machine and printed, and a good printed matter was obtained.

[Example 2] In the thermal development of Example 1,
An image was formed in the same manner as in Example 1 except that the surface (sheet side) of the light-sensitive material was brought into close contact with a hot plate heated to 135 ° C. and heat-developed for 20 seconds. A printed matter was obtained. Also, handling of the light-sensitive material was as easy as in Example 1.

[Comparative Example 1] In the thermal development of Example 1,
Except that the surface of the photosensitive material was heat-developed without being covered with a sheet,
When an image was formed in the same manner as in Example, an image and a printed matter substantially similar to those in Example 1 were obtained. However, the surface of the photosensitive material was sticky because of liquid paraffin, and the handling of the photosensitive material was troublesome.

[Comparative Example 2] The light-sensitive material of Example 1 was imagewise exposed in the same manner as in Example 1, and then a layer of liquid paraffin having a thickness of about 1 mm was provided on the surface of a hot plate heated to 135 ° C. The surface of the light-sensitive material was brought into close contact with it and heat-developed for 20 seconds. After that, when the same processing and printing as in Example 1 were performed, almost the same image and printed matter as in Example 1 were obtained. However, the surface of the hot plate was sticky because of liquid paraffin, and the handling of the photosensitive material was troublesome.

[Comparative Example 3] In the thermal development of Example 1,
Images were formed in the same manner as in Example except that the surface of the light-sensitive material was thermally developed without forming a layer of liquid paraffin, and the obtained image was slightly uneven as compared with the image of Example 1. The peripheral part did not cure sufficiently.

[Comparative Example 4] Using the light-sensitive material of Example 1,
After imagewise exposure as in Example 1, the surface of the light-sensitive material was brought into close contact with the surface of a hot plate heated to 135 ° C. without providing a liquid paraffin layer, and heat development was performed for 20 seconds. After that, when the same processing and printing as in Example 1 were performed,
The obtained image was slightly uneven as compared with the image of Example 1, and especially the peripheral portion was not sufficiently cured. It was

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view for explaining one embodiment of heat development of the present invention.

FIG. 2 is a schematic cross-sectional view for explaining another aspect of heat development of the present invention.

[Explanation of symbols]

 11 Hot Plate 12 Support 13 Photosensitive Polymerizable Layer 14 Applied Liquid 15 Sheet 21 Hot Plate 22 Sheet 23 Applied Liquid 24 Photosensitive Polymerizable Layer 25 Support

Claims (1)

[Claims] 1. A photosensitive material, which comprises a support and a photosensitive polymerizable layer containing a silver halide, a reducing agent and a polymerizable compound, is imagewise exposed, and then a liquid is applied onto the photosensitive polymerizable layer. Then, the photosensitive polymerizable layer is covered with a sheet, and in that state, the photosensitive material is heated at a temperature of 60 ° C. or higher to thermally develop the silver halide, and the polymerizable compound is imagewise cured to form a polymer image. Forming method for forming a film.