JP2001294621A - Polymer, polymer composition and sheet material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer capable of producing a film having low water permeability and a low water content and a sheet material having a layer containing the polymer and to provide a method for heat-treating the sheet material. SOLUTION: This polymer is constituted of a monomer unit represented by general formula (1) (W1 is H, an alkyl group, an aromatic group or a heterocyclic group; Y1 is a bifunctional connecting group; V is a water retaining group which is at least partially gasified by heating and vanished). The sheet material has a layer containing the polymer. The method for heat-treating the sheet material is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer capable of reducing water retention by heating and a composition containing the polymer. Further, the present invention relates to a sheet material having a layer of a composite composition containing the polymer.

[0002]

2. Description of the Related Art Sheet materials are used for various purposes such as packaging materials for various products, printing materials for displaying tangible and intangible product information, and radiation recording materials for displaying medical images. Sheet materials used as packaging materials are required to block moisture from the outside world and improve the preservability of the package, and barrier materials have been developed to reduce the permeability and retention of moisture. Have been. Polyethylene sheets and polypropylene sheets have low moisture permeability and low moisture content, and are excellent as barrier materials.However, since thin films have insufficient strength, packaging materials include polycarbonate sheets, polyethylene terephthalate sheets or high elastic modulus sheets. A polyethylene terephthalate sheet or the like is used.

[0003] However, although they are satisfactory in strength, they are not sufficient in terms of moisture barrier properties and water content to satisfy the performance as a packaging material. A method of applying a barrier composition to these sheet materials to increase the moisture barrier property has been performed. As the sheet material having the barrier composition applied to enhance the moisture barrier property, for example, vinylidene chloride is applied. Polyethylene terephthalate sheet, polyethylene terephthalate sheet and the like.

In recent years, the use of chlorine-based barrier materials tends to be avoided because they cause environmental destruction. For this purpose, other materials have been demanded, but no satisfactory material has been found. Therefore, there is a demand for a polymer composition which has moisture barrier properties after drying, can suppress moisture permeability, can reduce the water content in the system, and has good coatability.

[0005] The permeability of water and the retention of water not only affect the preservability, but also the dimensional change of the sheet material due to the change in the water content in the resin due to the absorption of moisture. In the field of image forming materials, a dimensional change of a sheet material due to the absorption of moisture causes deformation of an image, so that a technique for controlling moisture is also required in the field of image forming materials. In order to avoid these problems, technology development has been promoted to use as little material as possible which is susceptible to moisture, but there are limitations.

An image recording material obtained by coating a silver halide or an organic silver salt on a sheet material is used for a printing material or a radiation recording material. These image recording materials form an image using a light-heat reaction, but the reaction is easily affected by moisture. Therefore, in order to make the performance less affected by moisture as much as possible, additives called inhibitors or stabilizers are used, but they are not sufficient. In addition to the means for making the image recording material less susceptible to the influence of water, it is necessary that no water is contained in the image recording material and that no water is contained.

In recent years, photosensitive materials capable of forming an image by light or heat do not emit waste liquid during development processing, do not pollute the environment, and are excellent in workability. It is spreading rapidly. An image recording material capable of forming an image by light or heat includes an image forming layer provided on the front surface side, a protective layer for protecting the image forming layer, and an irradiation prevention layer (AH).
Layer) and a backing layer (BC
Layer) and a layer such as a protective layer for the backing, and the materials constituting these layers are all sensitive to the presence of moisture, and the moisture is removed before or after the development processing. It is imperative that they be shut off and not affected by moisture.

Therefore, after the above-mentioned constituent layers constituting the image recording material are obtained by drying, a water-dispersible hydrophobic polymer which can be coated with a polymer composition having a low water content has been sought. Was. The water-dispersible hydrophobic polymer is
It is necessary to be stably dispersed in water,
After being applied and dried to form a film, the composition is adjusted so that the moisture permeability and the water content are reduced.

In order to stably disperse in water, a hydrophobic polymer which has been polymerized using a small amount of a monomer unit of a hydrophilic group to impart hydrophilicity is used.
Since the hydrophilic group used to enhance the stability of the water dispersion is present even after coating and drying, it functions to retain water, and also forms a passage for passing water, The dried coating film tends to absorb moisture. This impairs the curl and dimensional stability of the photosensitive material, and the moisture present in the system weakens the adhesive strength between the support and the photosensitive layer, the photosensitive layer and the protective layer, and other layers. It will bring disadvantages. Further, the presence of moisture deteriorates the photographic performance and deteriorates the storability of the image recording material.

In order to improve the adhesive strength between the layers, techniques have been developed to crosslink the binder used for forming the layers between the layers and to promote the crosslinking between the support and the binder. It has become available. However, highly reactive cross-linking agents are problematic in terms of handling them, and it is necessary to develop technologies that reduce the amount of use as much as possible or technologies that do not use them. ing.

As a method of improving the adhesion between layers, corona discharge treatment, plasma treatment, or the like is used. However, if a strong corona treatment or plasma treatment is carried out to strengthen interlayer adhesion, a part of the film surface is destroyed, It causes defects such as contamination by broken powder and uneven surface. Therefore, by processing under appropriate conditions,
There is a need for a material that increases the adhesive strength between layers.

[0012]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a polymer capable of obtaining a membrane having low water permeability or low water content. A second object of the present invention is to provide a sheet material having a layer that can be a layer having low water permeability or a low water content. A third object of the present invention is to provide excellent storage stability,
An object of the present invention is to provide a sheet material having a layer containing a silver halide and an organic silver salt which does not adversely affect photographic performance.

[0013]

The object of the present invention is to provide: (1) a polymer characterized in that at least a part of the monomer unit is constituted by a monomer unit represented by the general formula (1): .

[0014]

Embedded image (Wherein, W ¹ represents a hydrogen atom or an alkyl group, an aromatic group, or a heterocyclic group, each of which may have a substituent;
¹ represents a divalent linking group, and V represents a water-retaining group which is at least partially vaporized by heating and disappears. (2) In the general formula (1), at least a part represented by V is vaporized by heating and disappears.
The polymer according to the above (1), wherein at least a part of the polymer is a water-retaining group which is eliminated by heating to carbon dioxide gas. (3) In the general formula (1), at least a portion represented by V is vaporized by heating and disappears,
The polymer according to the above (1) or (2), which is a water-retaining group forming a salt with the ions represented by the general formulas (a) to (c).

[0015]

Embedded image (In the general formulas (a) to (c), R ^{1 to} R ⁷ each represent a hydrogen atom or an alkyl group, an aromatic group, or a heterocyclic group which may have a substituent, and Z ¹ , Z ² and Z ³ represents a group of atoms necessary to form a 4- to 8-membered ring containing a quaternary nitrogen, and the ring formed by the group of atoms represented by Z ¹ , Z ² and Z ³ represents a substituent. L ¹ represents a divalent linking group, and n represents an integer of 1 to 20.) (4) Composition containing the polymer according to any one of the above (1) to (3) A sheet material having an object layer. (5) The sheet material according to (4), which has been subjected to corona discharge treatment or plasma treatment. (6) The sheet material as described in (4) or (5) above, wherein a layer containing silver halide grains is provided. (7) The sheet material as described in any of (4) to (6) above, wherein a layer containing an organic silver salt is provided. (8) A heat treatment method, wherein the sheet material according to any of (4) to (7) is heat-treated at a temperature in the range of 80C to 400C. Is achieved by

Hereinafter, the present invention will be described in detail. First, the polymer of the present invention in which at least a part of the monomer unit is constituted by the monomer unit represented by the general formula (1) (hereinafter, sometimes referred to as the polymer of the present invention) will be described. Even if the polymer of the present invention is a polymer composed only of the monomer unit represented by the general formula (1),
Further, a copolymer containing the monomer unit represented by the general formula (1) as a comonomer may be used. Next, the monomer unit represented by the general formula (1) of the present invention (hereinafter, sometimes referred to as the monomer unit of the present invention) will be described.

[0017]

Embedded image (Wherein, W ¹ represents a hydrogen atom or an alkyl group, an aromatic group, or a heterocyclic group, each of which may have a substituent;
¹ represents a divalent linking group, and V represents a water-retaining group which is at least partially vaporized by heating and disappears. )

In the general formula (1), in the optionally substituted alkyl group, aromatic group and heterocyclic group represented by W ¹ , the alkyl group may be a straight-chain or straight-chain having 1 to 30 carbon atoms. A branched alkyl group is preferable, and examples thereof include a methyl group, an ethyl group, a butyl group, a pentyl group, a heptyl group, an octyl group, a dodecyl group, an isopropyl group, an isooctyl group, an isononyl group, an ethoxypropenyl group, and a butoxyethyl group. Can be Examples of the aromatic group include, for example, a phenyl group and a naphthyl group.Examples of the heterocyclic group include a pyridyl group, a furyl group, a thiophenyl group, a pyrimidyl group, an imidazole group, a thiazole group, an oxazole group, and a triazole. Group, tetrazole group and the like.

Examples of the substituent which the alkyl group, the aromatic group and the heterocyclic group may have include, for example, a halogen atom (for example, chlorine, bromine and fluorine), a halogen-substituted alkyl group ( For example, trifluoromethyl group, perfluorobutyl group, perfluorooctyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, butoxy group, octoxy group, etc.), hydroxy group, cyano group, amino group, substituted amino group (Eg, methylamino group, dimethylamino group, ethylamino group, phenylamino group, etc.), substituted oxy group (eg, ethyloxy group, polyethyleneoxy group, polypropyleneoxy group, polybutyleneoxy group, phenoxy group, etc.),
Examples include a cyano group, an alkylthio group (for example, a methylthio group, an ethylthio group and a butylthio group), a vinyl group, and an acetyl group.

Examples of the divalent linking group represented by Y ¹ include, for example, an alkylene group (eg, an ethylene group, a butylene group, an octylene group, an isobutylene group, a 2-hydroxypropylene group) and a divalent aromatic group (Eg, phenylene group, naphthylene group, etc.), divalent heterocyclic group (eg, divalent group from pyridine, furan, pyrimidine, thiophene, oxazole, imidazole, triazole, thiazole, pyrrolidine, etc.), ester group (eg, , -CO
OA-), an ether group (for example, -OA-), an amino group (for example, -NHA-) and the like. Here, A represents a divalent linking group, and examples thereof include the aforementioned alkylene group, divalent aromatic group, and heterocyclic group.

At least a part of the water-retaining group represented by V is vaporized by heating and disappears by heating, and at least a part of the group is vaporized by heating to lose water permeability or water storage property. The polymer has a function of lowering the water permeability or water storage property of the polymer, and is not particularly limited as long as it has such a function, but is preferably a group represented by the following formula.

Where B represents an electron-withdrawing group, Q represents a group capable of decarboxylation by heating, and M represents a divalent linking group for linking B and Q. Represent.

The electron-withdrawing group represented by B is
For example, SO ₂ , an aromatic group substituted with a halogen, a cyano group, or the like (eg, a phenylene group or a naphthylene group) may be mentioned.
For _{example, -CH 2 COOH, -CH (Cl} ) COOH or salts thereof, and the like. Examples of the divalent linking group linking B and Q represented by M include an alkylene group (for example, a methylene group, an ethylene group, a butylene group, an octylene group, an isobutylene group, a 2-hydroxypropane group, a tert-butylene group) And the like).

The loss of water permeability or water preservability of the polymer of the present invention is not due to cross-linking or blocking, but to the loss of a part of the group represented by V by gasification. is there. However, not all of the loss of water permeability or preservation of the polymer need to be brought about by gasification, and some may be brought about by other means, such as the use of crosslinkers or blocking agents. Good. less than,
Preferred specific examples of the monomer represented by the general formula (1) are shown.

[0025]

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[0026]

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[0027]

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The monomer represented by the general formula (1) may be a salt. As the salt, an alkali metal (sodium,
Salts with alkaline earth metals (calcium, magnesium, etc.), quaternary ammonium compounds and the like. Particularly preferred salts are salts with quaternary ammonium ions, and are represented by the following general formulas (a) to (a).
A salt with the ion represented by (c) is preferred.

[0029]

Embedded image (In the general formulas (a) to (c), R ^{1 to} R ⁷ represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic group, or a heterocyclic group, and Z ¹ , Z ² and Z ³ represents a group of atoms necessary to form a 4- to 8-membered ring containing a quaternary nitrogen, and the ring formed by the group of atoms represented by Z ¹ , Z ² and Z ³ represents a substituent. L ¹ represents a divalent linking group, and n represents an integer of 1 to 20.)

In the general formulas (a) to (c), R ^{1 to} R ⁷
Examples of the alkyl group which may have a substituent represented by
For example, methyl group, ethyl group, butyl group, octyl group,
A dodecyl group, a 2-hydroxybutyl group, a 2-chlorooctyl group and the like are mentioned, and an aromatic group which may have a substituent includes, for example, a phenyl group, a naphthyl group and a 4-methoxyphenyl group. Examples of the heterocyclic group which may have a substituent include a pyridine ring group, a pyrimidine ring group, an imidazole ring group, a thiazole ring group, and an oxazole ring group.

The 4- to 8-membered ring containing a quaternary nitrogen formed by the group of atoms represented by Z ¹ , Z ² or Z ³ may have a substituent. Examples include the substituents described in the description of the substituents represented by R ^{1 to} R ⁷ . The divalent linking group represented by L ¹ is not particularly limited, and examples thereof include a divalent group such as an alkylene group, a phenylene group, and a naphthylene group, and a group obtained by combining these groups. Further, these divalent linking groups may be substituted with a halogen atom, the substituents described in the description of the substituents represented by R ^{1 to} R ⁷ , and the like. The general formulas (a) to (a)
Preferred examples of the ion represented by (c) are shown below.

[0032]

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[0033]

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[0034]

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The counter ion in the salt of the polymer of the present invention is not particularly limited. When the counter ion is a basic group, at least a part of the counter ion is changed from the water-retaining group represented by V by heating. After gasification and disappearance, a base remains, and the base becomes basic by the base, thereby stabilizing the resin. Also, a gasifying base can be used to avoid making it basic. When the polymer of the present invention is an ammonium salt, there is an advantage that ammonia is gasified and disappears by heating, so that the ion of the monomer can be stabilized and removed after the heat treatment.

The monomer unit of the present invention may be added to commercially available monomers such as methacrylic acid, acrylic acid, itaconic acid, maleic acid, vinyl alcohol, allylamine, styrene, vinyl acetate, etc. It can be easily obtained by adding or condensing a holding group. Further, the water-retaining group, which is at least partially gasified by heating and disappears, can be easily synthesized by a known technique. The salt of the monomer unit of the present invention is prepared using an alkali metal salt, alkaline earth metal salt, quaternary ammonium hydroxide, halide (chloride, bromide, iodide, etc.) having a corresponding counter ion. It can be obtained by salting. The by-product generated by the synthesis reaction is removed when it does not hinder the reaction, but may be used as it is in the polymerization when it does not hinder the reaction.

The fact that the composition of the present invention has water retention means that the composition of the present invention is applied to the surface of a glass plate and dried to form a thin film. After the plasma treatment, it can be detected by measuring the water content. The water content is represented by the ratio of the mass of the contained water to the mass of the thin film. In addition, the water content can be determined by measuring with a Fischer-type moisture meter, which is a simple measuring device. Examples of the comonomer to be copolymerized with the monomer unit of the present invention include acrylic monomers, styrene monomers, vinyl acetate monomers, butadiene monomers, and acrylonitrile monomers.

The polymer of the present invention is obtained by mixing the monomer unit of the present invention alone or together with a comonomer in water,
It can be obtained by polymerizing at 30 ° C. to 100 ° C. for 10 minutes to 24 hours in the presence of a commercially available polymerization initiator. Particularly preferred polymerization temperature and time are 50 ° C. ± 1.
0 ° C., 5 hours ± 2 hours. Table 1 shows specific examples of the polymer of the present invention with the composition, composition ratio, and molecular weight of the monomers used to obtain the polymer.

[0039]

[Table 1]

In Table 1, styrene is St, methyl acrylate is MA, methyl methacrylate is MMA, ethyl acrylate is EA, butyl acrylate is BA,
Hexyl acrylate HA, octyl acrylate OA, butadiene Bu, cyanoethyl acrylate CA, cyclohexenyl acrylate CH, cyclohexyl acrylate CHA, cyclohexyl methacrylate CMA, vinyl acetate VA, acrylonitrile AN, vinyl chloride VC, VD of vinylidene chloride
C, hydroxyethyl acrylate is abbreviated as HEA, and hydroxyethyl methacrylate is abbreviated as HEMA. Also,
The fifth component is a monomer unit represented by the general formula (1) of the present invention, and is shown by the example number of a specific example of the monomer unit represented by the general formula (1) described above. In addition, the content was shown by mass percentage.

Table 2 shows specific examples of the polymer of the present invention in which a salt is formed with an equimolar counter ion. In addition, the counter ion used was shown by the example number of the specific example of the ion represented by general formula (a)-(c) described above.

[0042]

[Table 2]

The sheet material of the present invention may be composed of only the layer of the composition containing the polymer of the present invention, or may be formed by forming a layer of the composition containing the polymer of the present invention on a sheet substrate. May be done. The sheet material in which the layer of the composition containing the polymer of the present invention is formed on the sheet substrate can be obtained by applying a coating solution in which the polymer of the present invention is dissolved or dispersed in a solvent to the sheet substrate. . Examples of the solvent that can be used include alcohols (eg, methanol, ethanol, butanol, fluorinated alcohol, amyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), amines (eg, Polyvinylpyrrolidone, polyethyleneimine, pyridine and the like), dimethylsulfoxide, dimethylformamide, dioxolan, cyclohexanone and the like.

The layer formed by coating may be any of the layers formed on the sheet base, and may be formed directly on the sheet base or formed on the sheet base. It may be formed on another layer. Further, there may be a plurality of layers formed by applying the composition containing the polymer of the present invention.

The layer formed by coating the composition containing the polymer of the present invention is preferably provided in a sheet material having a layer containing silver halide grains and an organic silver salt. In the above sheet material, in addition to the layer containing silver halide grains and the organic silver salt, various layers such as an undercoat layer, an antihalation (AH) layer, a filter layer, an intermediate layer,
A protective layer, an intermediate layer, and a back coat (BC) layer can be provided.

The sheet material provided with the layer containing the silver halide grains and the layer containing the organic silver salt of the present invention can be an image forming material such as a photosensitive material.

In a sheet material provided with a layer containing silver halide grains and a layer containing an organic silver salt, any of the constituent layers may be a layer coated with the composition containing the polymer of the present invention. The protective layer of the layer containing the silver halide grains, the organic silver salt, and the back coat (BC) layer is preferably a layer formed by coating the composition containing the polymer of the present invention. When the layer formed by applying the composition containing the polymer of the present invention is a protective layer, the polymer of the present invention is 0.01 mg.
Is preferably used in an amount of to 10 g / m ^2, particularly preferred range is 0.1mg~1g / m ^2. When contained in a layer other than the protective layer, 0.02 to 0.6 g / m ²
Is preferable.

The silver halide used in the present invention can be prepared by any method known in the field of photographic technology such as a single jet or double jet method, for example, a method such as an ammonia emulsion, a neutral method or an acid method. Can be prepared.

The grain size of the silver halide grains is preferably small in order to obtain good image quality, and the average grain size is 0.1 μm or less, more preferably 0.01 μm or less.
To 0.1 μm, particularly preferably 0.02 μm to 0.08
μm. The shape of the silver halide grains is not particularly limited, and may be a cubic or octahedral so-called normal crystal, a spherical shape other than the normal crystal, a rod shape, a plate shape, or the like. The silver halide grain composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide.

The photosensitive silver halide prepared by the above-mentioned various methods can be chemically enhanced by, for example, a sulfur-containing compound, a gold compound, a platinum compound, a palladium compound, a silver compound, a tin compound, a chromium compound or a combination thereof. I can feel it. For methods and procedures for chemical sensitization, see, for example, US Pat.
0, British Patent 1,518,850,
These are described in JP-A-51-22430, JP-A-51-78319, and JP-A-51-81124, and these methods and means can be used also in the chemical sensitization of the silver halide of the present invention.

These photosensitive silver halides include:
Metals belonging to Groups 6 to 10 of the Periodic Table of the Elements for illuminance failure and gradation adjustment, for example, Rh, Ru, Re, I
An ion such as r, Os, and Fe, a complex thereof, or a complex ion can be contained. In particular, it is preferable to contain an ion or a complex ion of a metal belonging to Groups 6 to 10 of the periodic table.

The above metals include W, Fe, Co, N
i, Cu, Ru, Rh, Pd, Re, Os, Ir, P
Preferably, t and Au are used. In particular, when used for a photosensitive material for plate making, it is preferably selected from Rh, Re, Ru, Ir and Os. These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a six-coordinate complex.

The content of metal ions or complex ions is generally 1 × 10 ⁻⁹ per mole of silver halide.
~ 1 × 10 ^-2 mol is suitable, preferably 1 × 10 ^-8 mol.
１1 × 10 ^-4 mol. The compound which provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into silver halide grains, and preparation of silver halide grains, that is, nucleation, growth, and physical ripening , May be added at any stage before and after chemical sensitization, in particular, nucleation, growth, preferably added at the stage of physical ripening, more preferably nucleation, added at the stage of growth, Most preferably, it is added at the stage of nucleation. At the time of addition, it may be added in several portions.

The metal ions or complex ions can be uniformly contained in the silver halide grains, and are disclosed in JP-A-63-29603, JP-A-2-306236, JP-A-3-167545 and JP-A-3-167545. As described in JP-A-4-76534, JP-A-6-110146, JP-A-5-273683 and the like, the particles can be contained in the particles with distribution. Preferably, it is contained in the particles with a distribution.

The metal compound used can be added by dissolving it in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method of adding an aqueous solution of a metal compound as a third aqueous solution when a silver salt solution and a halide solution are simultaneously mixed, wherein an aqueous solution of a metal compound is added to a water-soluble silver salt solution or a water-soluble halide solution for forming particles. A method of preparing silver halide grains by a three-liquid simultaneous mixing method, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, and doping a metal ion or complex ion in advance during silver halide preparation. There is a method of adding another silver halide grain and dissolving it to prepare silver halide. In particular, a method in which an aqueous solution of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution and used.

At the time of addition to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening. The silver halide thus prepared in advance can be mixed with other components and introduced into the composition used in the present invention.

The organic silver salt used in the present invention includes, for example, silver salts of fatty acids having 16 to 28 carbon atoms. In particular, needles such as silver behenate, silver arachidate and silver stearate are used. Shaped crystals are preferred. The sheet material provided with the layer containing the organic silver salt of the present invention can be a photothermal or hot-wire type material.

As is well known in photosensitive silver halide grains, the inverse relationship between the size of crystal grains and their covering power also holds for photothermal and hot-wire type materials. Therefore, when the organic silver salt particles are large, the covering power is small and the image density is low, so that it is preferable to reduce the size of the organic silver salt. In the present invention, the organic silver salt particles have a minor axis of 0.01 μm or more and 0.2 μm or more.
0 μm or less, the major axis is preferably from 0.10 μm to 5.0 μm, and the minor axis is from 0.01 μm to 0.15 μm.
μm or less, and the major axis is more preferably 0.10 μm or more and 4.0 μm or less.

The particle size distribution of the organic silver salt is preferably monodispersed. When the particles of the organic silver salt have the form of particles having a short axis and a long axis as described above, the particle size distribution of the organic silver salt is monodisperse, and the short axis and the long axis each have a standard length. Deviation is obtained, and a value obtained by dividing the average value of each of the short axis and the long axis by 100% (monodispersity%) is 80% or less. More preferred monodispersity is 60%
Or less, more preferably 40% or less. The shape of the organic silver salt can be determined from a transmission electron microscope image of the organic silver salt dispersion.

As another method for measuring the monodispersity, there is a method in which the standard deviation of the volume-weighted average diameter of the organic silver salt is determined. It is obtained as a 100-percent (coefficient of variation%) value divided by the diameter.

The organic silver salt of the present invention has the above coefficient of variation (%)
In other words, it is preferably 80% or less, more preferably 60% or less.
%, More preferably 40% or less. The above-mentioned coefficient of variation is obtained, for example, by irradiating laser light to organic silver salt particles dispersed in a liquid, mathematically calculating the fluctuation of the scattered light to determine the particle size (volume weight average diameter), and obtaining the obtained particles. It can be determined from the size (volume weight average diameter).
In the present invention, the organic silver salt is generally 0.1 to 5 g.
Is preferably employed in the range of / m ^2, more preferably it is 1 to 3 g / m ^2.

When a photosensitive silver halide is used together with an organic silver salt in a photothermal or hot-wire type material, it is preferable that the photosensitive silver halide and the organic silver salt be sufficiently contacted. In order to sufficiently contact the photosensitive silver halide with the organic silver salt, a part of the organic silver salt is converted into the photosensitive silver halide by the silver halide forming component to form the silver halide. Is also good. When a part of the organic silver salt is converted into a photosensitive silver halide by a silver halide forming component,
As described in U.S. Pat. No. 3,980,482, a low molecular weight amide compound may be used in order to achieve sensitization.

In order to sufficiently contact the photosensitive silver halide with the organic silver salt, a protective polymer for preparing the photosensitive silver halide may be used, for example, US Pat. No. 3,706,564. Specification, No. 3,706,565
No. 3,713,833, No. 3,
748,143, British Patent 1,362,97
Means using a polymer other than gelatin such as polyvinyl acetal described in the specification of British Patent No.
Means for enzymatically decomposing gelatin used for the preparation of the photosensitive silver halide emulsion described in JP-A-354,186. Further, a means for omitting the use of a protective polymer by preparing photosensitive silver halide grains described in U.S. Pat. No. 4,076,539 in the presence of a surfactant can also be applied. .

When a part of the organic silver salt is converted to the photosensitive silver halide by the silver halide forming component in order to sufficiently bring the photosensitive silver halide into contact with the organic silver salt, an organic compound prepared beforehand is used. A silver halide forming component can be applied to a solution or dispersion of a silver salt or a sheet material containing an organic silver salt to convert a part of the organic silver salt into photosensitive silver halide. The silver halide thus formed is in effective contact with the organic silver salt and exhibits a favorable effect.

The silver halide forming component is a compound which can react with an organic silver salt to form a photosensitive silver halide.
Which compounds fall into this category and are effective can be determined by the following simple test. That is, after the organic silver salt and the compound to be tested are mixed and, if necessary, heated, the presence of a peak specific to silver halide is examined by X-ray diffraction. Silver halide-forming components that have been found to be effective by such tests include:
There are inorganic halides, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds, and specific examples thereof are described in U.S. Pat.
No. 09,039, 3,457,075, 4,003,749, British Patent 1,
498,956, JP-A-53-27027 and JP-A-53-25420 can be referred to.

These silver halide forming components are used in a small amount, not in a stoichiometric amount with respect to the organic silver salt. Usually, it is used in the range of 0.001 mol to 0.7 mol, preferably 0.03 mol to 0.5 mol, per 1 mol of the organic silver salt. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting a part of the organic silver salt into silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose. Usually, the reaction temperature is −23 ° C. to 74 ° C., and the reaction time is 0.1 second to 72 hours. The reaction pressure is preferably set at atmospheric pressure. This reaction is preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is 0.01 to 100 parts by mass, preferably 0.1 to 10 parts by mass per 1 part by mass of the organic silver salt.

It is preferable to incorporate a reducing agent into the photothermal and hot-wire type materials of the present invention. The reducing agent used here is any substance that reduces silver ions to metallic silver, and is preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are also useful as reducing agents, although hindered phenol reducing agents are preferred. The amount of the reducing agent used is from 1 to 10 of the organic silver salt layer.
% Is preferred. If the photothermal and hot-wire materials are of a multi-layer construction and the reducing agent is added to a layer other than the organic silver salt layer, a slightly higher percentage of about 2 to 15% is more desirable.

A general reducing agent can be used. For example, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2
-T-butyl-6-methylphenol), 1,1, -bis (2-hydroxy-3,5-dimethylphenyl)-
Ascorbic acid derivatives (for example, palmitic acid 1) such as 3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane
Aldehydes and ketones such as ascorbyl, ascorbyl stearate), benzyl and biacetyl,
3-pyrazolidone and indane-1,3-dione, etc.
Although tocopherol and the like can be used, a particularly preferred reducing agent is a bisphenol derivative. The amount of the reducing agent is preferably generally 0.1 to 15 g / m ^2, more preferably from 0.5 to 10 g / m ^2.

The polymer of the present invention can be used in combination with other materials. As a material to be used in combination, a material which is preferable in forming a field where silver halide, an organic silver salt and a reducing agent react is selected. Examples of these materials include hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, cellulose derivatives such as ethyl cellulose, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, sodium polyacrylate, polyethylene oxide, acrylamide-acrylate copolymer, Styrene-maleic anhydride copolymer, polyacrylamide, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, Styrene-butadiene-acrylic copolymer and the like can be mentioned.

The composition containing the polymer of the present invention preferably has a glass transition point of −60 ° C. to 80 ° C., particularly
50 ° C to 70 ° C is preferred. If the glass transition point is high, the temperature for thermal development becomes high, and if the glass transition point is low, fogging is liable to occur, resulting in a decrease in sensitivity and softness. When the composition containing the polymer of the present invention is an aqueous dispersion composition, it is preferably dispersed as fine particles having an average particle diameter in the range of 1 nanometer to several μm.

In the photothermal and hot-wire type materials of the present invention, it is preferable to include a matting agent in the protective layer and the BC layer on the image forming layer. The matting agent used in the present invention may be either an organic substance or an inorganic substance. Examples of the inorganic substance include silica described in Swiss Patent No. 330,158 and the like, and French Patent No. 1,296,995. Glass powder, British Patent No. 1,173,18
Examples of alkaline earth metals or carbonates such as cadmium and zinc described in the specification of JP-A No. 1 and the like, and organic substances include starch described in U.S. Pat. No. 2,322,037 and the like, and Belgian patent 625,451. Patent Specification and UK Patent No. 98
Starch derivatives described in the specification of Japanese Patent Publication No.
-3643, polystyrene or polymethacrylate described in Swiss Patent No. 330,158, etc., U.S. Pat.
Examples include polyacrylonitrile described in 79,257 and the like, and polycarbonate resin described in U.S. Pat. No. 3,022,169 and the like.

The shape of the matting agent may be either a fixed shape or an irregular shape, but is preferably a fixed shape, and a spherical matting agent is preferred. The particle size of the matting agent is represented by the diameter of a sphere having the same volume as the volume of the matting agent particles (diameter converted into a sphere). In the description of the present invention, the particle size of the matting agent refers to the diameter converted into a sphere. The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm.
The monodispersity of the particles is preferably 50% or less, more preferably 40% or less, and particularly preferably 20% or less. Here, the monodispersity of particles refers to a value obtained by dividing the standard deviation of the particle size distribution by the average value of the particle sizes and multiplying the result by 100. The matting agent may be contained by dispersing in a coating solution in advance and applying it. Alternatively, after applying the coating solution, the matting agent may be contained by spraying before the end of drying. Also,
When a plurality of types of matting agents are added, both methods may be used in combination.

The sheet material of the present invention in which the layer containing silver halide grains and the layer containing an organic silver salt are the photosensitive layer is classified into two types: an exposure wet development type and a dry type. The latter is a photothermal type or a hot-wire type. Divided into The wet-type sheet material is a material that forms a latent image on silver halide with light and develops with a developing solution and a fixing solution dissolved in water to form a photographic image. For example, reducible organic silver salts,
This is a material in which a photosensitive layer is formed in a state where a catalytically active amount of silver halide, a hydrazine derivative, a reducing agent and, if necessary, a color tone suppressing color tone agent are dispersed in a binder.

The photothermal sheet material is a material which is stable at normal temperature, but is developed by being heated to a high temperature (for example, 80 ° C. to 200 ° C.) after exposure. The hot-wire type sheet material is used for simultaneous exposure and heating.
Heated to 400 ° C. Heating includes a one-step method of heating at a constant temperature for a fixed time after exposure, and a method of stepwise heating such as preheating, main heating and post-heating. To simultaneously perform exposure and heating, it is preferable to use a heat ray such as a YAG laser. The irradiation time is set to a short time of 10 ^-4 seconds to 10 ^-9 seconds, and the heat ray is irradiated. Depending on the method of selecting the material of the image forming layer, there are two types: a photothermal type in which development is performed by heating after exposure, and a hot-wire type in which development is performed by simultaneously performing exposure and heating.

In the present invention, all exposures are preferably performed by laser scanning exposure. However, laser scanning exposure in which the angle between the exposure surface of the photothermal type material or the hot-wire type material and the scanning laser beam does not become substantially perpendicular to each other is preferred. It is preferable to use a machine. Here, "not substantially perpendicular" means that the angle is most perpendicular during laser scanning, preferably 55 degrees or more and 88 degrees or less, more preferably 60 degrees or more and 86 degrees or less, still more preferably. 65 degrees or more 84
Degrees, most preferably 70 degrees to 82 degrees.

The beam spot diameter on the exposed surface of the photothermal or hot-wire material when the laser beam scans the photothermal or hot-wire material is preferably 200 μm or less, more preferably 100 μm or less. It is preferable that the spot diameter is small in that the shift angle of the laser incident angle from the perpendicular can be reduced. Note that the lower limit of the beam spot diameter is 10 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration caused by reflected light such as occurrence of interference fringe-like unevenness. Exposure is preferably performed using a laser scanning exposure machine that emits a scanning laser beam in which a plurality of wavelength lights are superimposed.
As compared with a single mode scanning laser beam, it is possible to reduce the deterioration of image quality due to the occurrence of unevenness of exposure and unevenness like interference fringes.

As a method of superimposing a plurality of wavelengths, there are a method using a synthetic wave mixed wave, a method using return light via a reflection mirror, and a method using high frequency superposition. The superimposed wave has a single exposure wavelength, and usually has an exposure wavelength distribution of 5 nm or more, preferably 10 nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm. At the time of superimposition, it is preferable to control the intensity and amplitude of the laser beam and synthesize the laser beams. Photothermal materials are organic silver salts when heated (act as an oxidizing agent)
It is a material that promotes an oxidation-reduction reaction between a metal and a reducing agent to generate metallic silver. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide by exposure.

The hot-wire type material is different from the photothermal type material in that the organic silver salt is converted into metallic silver by heat without using silver halide in the photosensitive layer. In both photothermal and hot-wire materials, the silver formed by the reaction of the organic silver salt in the exposed areas forms a black image, which forms an image that is clearly distinguished from the unexposed areas. This reaction process proceeds without supplying a processing liquid such as water from the outside.

It is preferable to add a color tone agent to the photothermal and hot-wire type materials of the present invention. Examples of suitable toning agents are R
No. 17029, which includes the following: Phthalazinone, phthalazinone derivatives or metal salts of these derivatives (for example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone and 2,3-dihydro-1,4-polyhalomethane Compound dione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + p
A combination of a polyhalomethane compound and phthalic acid; a polyhalomethane compound (including an adduct of the polyhalomethane compound) and maleic anhydride and phthalic acid, 2,3-naphthalenedicarboxylic acid or o.
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naphthoxazine derivatives, benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (Eg, 2,4-dihydroxypyrimidine); tetraazapentalene derivatives (eg, 3,6-
Dimercapto-1,4-diphenyl-1H, 4H-2,
3a, 5,6a-tetraazapentalene).

The photothermal and hot-wire type materials of the present invention include, for example, JP-A-63-159814 and JP-A-60-14.
Nos. 0335 and 63-231437 and 63
JP-A-2595651, JP-A-63-304242,
No. 63-15245, U.S. Pat. No. 4,639,4
No. 14, No. 4,740,455, No. 4,741,966, No. 4,751,175
And sensitizing dyes described in JP-A Nos. 4,835,096.

Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure It
em17643 IV-A (pp. 2 December 1978)
3), Item 1831X (August 1978, p. 4
Sensitizing dyes described in the documents described or cited in 37) can be mentioned. In particular, it is advantageous to select and use a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources.
Nos. 078, 9-54409 and 9-806
The compounds described in JP-A-79 are preferably used.

The support of the present invention may be a support such as paper, synthetic paper, nonwoven fabric, metal foil, polyester such as polyethylene terephthalate or polyethylene naphthalate, plastic film such as polycarbonate or polypropylene, or a composite sheet combining these. Supports can be used. One of the preferred embodiments of the layer structure of the photothermal and hot-wire type materials of the present invention is that an antihalation (AH) layer, a photosensitive layer, an intermediate layer, and a protective layer are sequentially formed on a support provided with an undercoat layer. It is a layer configuration provided in. Further, an undercoat layer may be provided on the opposite side of the support, and a photosensitive layer may be provided in the same layer configuration. An undercoat layer is provided on the opposite side of the support, and a conductive layer and a back coat (B
C) and a BC protective layer. These layers are preferably formed by simultaneous multi-layer coating using a known technique.

The support used for the sheet material of the present invention is preferably subjected to a corona discharge treatment or a plasma treatment in order to improve the adhesiveness. Corona discharge devices and plasma generators used for corona discharge treatment and plasma treatment are described in literatures and are commercially available. The corona discharge treatment and the plasma treatment can be performed by using a corona discharge device or a plasma generator described in these documents or commercially available. Corona discharge can be generated by applying a DC voltage of 1,000 to several thousand volts to a needle-like or wire-like electrode. The degree of treatment of the sheet material can be adjusted by the speed of passage through the corona discharge surface and the output of the discharge.
A preferred range for the degree of treatment is 1 microwatt / m ·
Min to 1 MW / m · min, particularly preferably
It is 1 watt / m · min to 100 watt / m · min. A method of applying a voltage between the electrodes includes a simple direct current type, a rectangular wave type, a high frequency superposition type, and the like, and any of them may be selected.

In the plasma processing, plasma is generated, and processing is performed using the generated plasma. Plasma can be generated by discharging to a region where plasma is generated by corona discharge under low pressure or normal pressure. Alternatively, the sheet surface may be modified by performing a plasma treatment using a microwave-excited plasma apparatus that guides and generates a microwave from a microwave generator through a waveguide. 0.5 MHz to 1
The surface of the sheet can be modified using high-frequency plasma generated at a high frequency of 0 MHz.

Processing conditions and the like can be determined with reference to pages 395 to 399 of the Plasma Material Science Handbook (published by Ohmsha on September 25, 1992), and the processing conditions of corona discharge can be applied, but it is particularly preferable. Is 1 mW / m
Min to 1 kW / mmin. The pressure of the atmosphere is preferably ^{1 × 10 -6 Pa~1 × 10 6} Pa, at close to atmospheric pressure can be introduced argon gas, nitrogen gas, the atmosphere of methane gas and the like. The pressure of the atmosphere for the plasma treatment is preferably as low as possible. In the case of treating the sheet material under reduced pressure, it is preferable to enclose a place where the sheet material is conveyed and to degas to 1 hPa to 1000 hPa.

For developing a sheet material having a photosensitive layer containing a silver halide emulsion of the present invention by a wet method, a commercially available developer or fixer commonly used can be used.
In addition, a developer and a fixing solution appropriately prepared to obtain proper photographic performance can also be used. To prepare a developer, it is preferable to use a combination of hydroquinone and its derivatives, methol and its derivatives, and phenidone and its derivatives as a developing agent. In particular, it is useful to use a combination of hydroquinone and a phenidone derivative. In the developer, a sulfite such as sodium sulfite, potassium sulfite, potassium metabisulfite, or the like can be used as an antioxidant. By using the sulfite in an amount of 0.25 mol to 2 mol per liter of the developing solution, a remarkable antioxidant effect is exhibited.

The developing solution may contain a water softener such as ethylenediaminetetraacetic acid or nitriloacetic acid, or an inorganic fog inhibitor such as potassium bromide or sodium chloride, for example, benzotrizole or benzotrizole. An organic fog inhibitor such as imidazoles can be contained. Further, glycols such as diethylene glycol and triethylene glycol, and amines such as diethanolamine and triethanolamine can be contained.

In order to adjust the pH of the developer, sodium hydroxide, potassium hydroxide or the like can be used as an alkali agent. When preparing a developer, it is preferable to use potassium ions.However, when potassium ions increase, a large amount of potassium ions used are brought into the fixing solution,
It is preferable that the ratio of sodium ions to potassium ions be in the range of 2: 8 to 8: 2 because the fixing speed becomes slow.

The developer can be adjusted by dissolving the components necessary for the development. However, it is also possible to prepare the components necessary for the development in advance and to dilute or dissolve the components before use. The form of the developer in which the components necessary for development are adjusted in advance may be in the form of a concentrate or a concentrated solution used during normal use, but may be in the form of a mixture of solid components, including glycols and amines. The form of an organic aqueous solution, the form of a viscous liquid in a semi-kneaded state having a high viscosity, the form of granules having a diameter of about 0.1 to 3 mm, and the diameter of 3 mm to 50 m
m in tablet form. These developers are diluted when used. The developer may be in a form used as prepared. The development temperature in the wet development processing may be in the range of 20 to 30 ° C. used for normal development, but may be set in the range of high temperature processing of 30 to 40 ° C. The processing time can be set in the usual range of 45 to 90 seconds, but is shorter.
It can be set to a quick process of ~ 45 seconds.

For the dry development, a commercially available developing machine for heat-generating materials can be used. The development temperature is preferably in the range of 80C to 400C. When the photosensitive material is a photothermal type in which an image is written with light and an image is formed with heat, the developing temperature is set to 80 ° C.
To 140 ° C., particularly 115 ° C.
Preheat for less than 30 seconds within 30 seconds,
It is preferable that the main development is carried out at a temperature of from 130 ° C to 130 ° C for 1 minute, and then cooled to a temperature of 80 ° C to 40 ° C within 30 seconds.

FIG. 1 shows an example of a developing machine suitably used for dry development. In FIG. 1, a film to be developed is sent from a film introduction unit 9 to a heat drum 4 by a group of introduction rollers arranged to pass through a preheating unit 7 provided with a heat source 5. The heat source 3 is disposed at the center of the heat drum 4, and the heat drum 4 is heated. The film sent to the heat drum 4 is arranged on the outer periphery of the heat drum 4, is brought into contact with the heat drum 4 by a group of pressing heat rollers 2, travels while being heated, and is cooled by a cooling unit 8 provided with a cooling source 6. And is discharged from the film discharge section. A heat drum heat insulating shield 1 is provided around the heat roller group 2 to prevent heat from being emitted to the outside.

As the heat source 5 of the preheating section 7 and the heat source 3 of the heat drum 4, a linear heat source such as a nichrome wire or a tungsten wire can be used. Further, a Peltier element or the like can be used as the cooling source 6 of the cooling unit 8. Further, as the cooling source 6, a cooling source used in a normal air conditioner can be used.

The surface of the heat-developable material in contact with the heat drum 4 may be a surface provided with a layer of a photosensitive emulsion or a surface provided with a back coat layer (BC). Can be selected according to Heat drum 4
The pressing and heat roller group 2 can be rotated in synchronization with each other, but the dimensional stability can be achieved by slightly controlling the number of rotations. As the heat source for heating the heat drum 4, a linear heat source such as the above-described nichrome wire or tungsten wire can be used, but it can also be heated by infrared rays, and has a built-in heater attached to the heat drum 4. It can also be heated by the sheet material.
Further, it is also possible to provide a cold mirror for reflecting heat rays on the heat drum 4 so as to adiabatically shield the heat drum and control the developing temperature.

[0094]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. Example 1 Synthesis of a monomer unit represented by the general formula (1) used for preparing the polymer of the present invention

Synthesis of Exemplified Monomer 1-1 72 g of acrylic acid and 216 g of 4-hydroxyphenylsulfonylacetic acid were added to 856 g of acetonitrile and mixed, and 6 g of 30% fuming sulfuric acid was added.
The reaction was performed at 6 ° C. for 6 hours. The precipitated product is separated by filtration and has a molecular weight of 2
194 g of the desired compound of 70.26 were obtained (yield: 72).
%). The measured elemental analysis values of the obtained compound and the theoretical values of Exemplified Monomer 1 are shown below. Actual elemental analysis values: C48.83, H3.90, O37.16, S12.40 Theoretical values C48.89, H3.73, O35.52, S11.86

Synthesis of Exemplified Monomer 1-3 72 g of acrylic acid and 204 g of 4-hydroxyfuranylsulfonyl acetic acid were added to 986 g of acetonitrile, mixed, and 6 g of 30% concentration fuming sulfuric acid was added.
The reaction was performed at 2 ° C. for 6 hours. The precipitated product is separated by filtration and has a molecular weight of 2
165 g of the target compound of 58.25 were obtained (yield: 64).
%). The measured elemental analysis values of the obtained compound and the theoretical values of Exemplified Monomer 3 are shown below. Actual elemental analysis value: C46.50, H3.91, O37.16, S12.40 Theoretical value C46.51, H3.90, O37.17, S12.42

Synthesis of Exemplified Monomer 1-6 In 879 g of acetonitrile, 72 g of acrylic acid and cyclopentadiene 2-hydroxy-4-sulfonylacetate 20
6 g was added and mixed, 3 g of fuming sulfuric acid having a concentration of 30% was added, and the mixture was reacted at 49 ° C. for 4 hours under a nitrogen atmosphere. The precipitated product was separated by filtration to obtain 174 g of the target compound having a molecular weight of 260.22 (yield 67%). Hereinafter, measured elemental analysis values of the obtained compound and theoretical values of Exemplified Monomer 6 are shown. Obtained elemental analysis value: C41.54, H3.10, O43.01, S12.30 Theoretical value C41.54, H3.10, O43.04, S12.32.

Synthesis of Exemplified Monomer 1-10 In a mixture of 889 g of acetonitrile, 72 g of acrylic acid and 2-
217 g of pyridine hydroxy-sulfonylacetate was added and mixed, 2.5 g of fuming sulfuric acid having a concentration of 30% was added, and the mixture was reacted at 53 ° C. for 4 hours under a nitrogen atmosphere. The precipitated product was separated by filtration to obtain 179 g of the target compound having a molecular weight of 271.25. (Yield 66%). The measured elemental analysis values of the obtained compound and the theoretical values of the exemplified monomer 10 are shown below. Found elemental analysis: C44.26, H3.34, N5.15, O35.38, S11.80 Theoretical C44.28, H3.34, N5.16, O35.39, S11.82

Synthesis of Exemplified Monomer 1-13 In 1020 g of acetonitrile, 72 g of acrylic acid and 4-
335 g of (4-hydroxyphenylcarbamide) phenylsulfonylacetic acid was added and mixed, 9.9 g of fuming sulfuric acid having a concentration of 30% was added, and the mixture was reacted at 42 ° C. for 7 hours under a nitrogen atmosphere. The precipitated product was separated by filtration to obtain 280 g of the target compound having a molecular weight of 389.38 (yield: 72%). Actual elemental analysis value: C56.56, H4.25, N3.47, O27.76, S7.74 Theoretical value C56.57, H4.25, N3.47, O27.76, S7.75

Example 2 Preparation of Aqueous Dispersion Solution of Polymer Preparation of Aqueous Dispersion Solution of Exemplified Polymer 101 300 g of ion-exchanged water was heated to 60 ° C., 9 g of potassium persulfate, and poly (oxyethylene) perfluorohexyl. After addition of 6 g of ether and 5 g of sodium salt of dodecylsulfonamidoethanesulfonic acid, 30 g of MMA, St
30 g, BA 20 g, EA 10 g and 10 g of Exemplified Monomer 1-1 were added over 1 hour. Then 87
C., the reaction was continued for 3 hours, and then cooled to room temperature in 10 minutes. The aqueous dispersion of the exemplary polymer 101 having the monomer composition and monomer content shown in Table 1 and having the molecular weight shown in Table 1 was carried out. A liquid was obtained.

Preparation of Aqueous Dispersion of Exemplified Polymer 102 Except that the monomer composition and monomer content were changed to those shown in Table 1, the same procedure as in the aqueous dispersion of Exemplified Polymer 101 was carried out. An aqueous dispersion of the exemplary polymer 102 having the molecular weight shown in the following was obtained.

Preparation of Aqueous Dispersion of Exemplified Polymer 103 300 g of ion-exchanged water placed in a 1-liter three-necked flask was heated to 60 ° C., and 8 g of potassium persulfate and poly (oxyethylene) perfluorohexyl ether were added. 5g,
After adding 6 g of dodecylsulfonamidoethanesulfonic acid sodium salt, 30 g of MMA, 40 g of BA, and EA2
4 g and 6 g of Exemplified Monomer 1-1 were added over 1 hour. Thereafter, the mixture was heated to 87 ° C. to continue the reaction for 3 hours, and then cooled to room temperature in 10 minutes. The exemplary polymer 103 having the monomer composition and the monomer content shown in Table 1 and having the molecular weight shown in Table 1 Was obtained.

Preparation of Aqueous Dispersion of Exemplified Polymers 104 to 109 In the same manner as the aqueous dispersion of Exemplified Polymer 103 except that the monomer composition and the monomer content were changed to those shown in Table 1, Aqueous dispersions of the exemplified polymers 104 to 109 having the molecular weights shown in Table 1 were obtained.

Preparation of Aqueous Dispersion of Exemplified Polymer 110 300 g of ion-exchanged water placed in a 1 liter stainless steel autoclave was heated to 60 ° C., and potassium persulfate 8 g and poly (oxyethylene) perfluorohexyl ether 5 g ,
After adding 6 g of dodecylsulfonamidoethanesulfonic acid sodium salt, 60 g of St, 38 g of liquefied Bu and 2 g of Exemplified Monomer 1-6 were added over 1 hour under a pressure of 2 MPa. Thereafter, the mixture was heated to 87 ° C. to continue the reaction for 3 hours, and then cooled to room temperature in 10 minutes. The exemplary polymer 110 having the monomer composition and monomer content shown in Table 1 and having the molecular weight shown in Table 1 was obtained. Was obtained.

Preparation of Aqueous Dispersion of Exemplified Polymers 111 to 115 In the same manner as in the aqueous dispersion of Exemplified Polymer 110, except that the monomer composition and the monomer content were changed to those shown in Table 1, An aqueous dispersion of the exemplary polymers 111 to 115 having the molecular weights shown in Table 1 was obtained.

Preparation of Aqueous Dispersion of Exemplified Polymers 116 to 120 In the same manner as in the aqueous dispersion of Exemplified Polymer 101, except that the monomer composition and the monomer content were changed to those shown in Table 1, An aqueous dispersion of the exemplary polymers 116 to 120 having the molecular weights shown in Table 1 was obtained.

Preparation of Aqueous Dispersion of Comparative Polymer k-1 300 g of ion-exchanged water was heated to 60 ° C., potassium persulfate 9 g, poly (oxyethylene) perfluorohexyl ether 6 g, dodecylsulfonamidoethanesulfonic acid After adding 5 g of sodium salt, 30 g of MMA, St
30 g, 20 g BA and 10 g EA were added over 1 hour. Thereafter, the mixture was heated to 87 ° C. to continue the reaction for 3 hours, and then cooled to room temperature in 10 minutes to obtain a comparative resin k
-1 was obtained.

Preparation of Aqueous Dispersion of Comparative Polymer k-2 300 g of ion-exchanged water placed in a 1-liter stainless steel autoclave was heated to 60 ° C., potassium persulfate 8 g, poly (oxyethylene) perfluorohexyl 5 g of ether,
After adding 6 g of sodium salt of dodecylsulfonamidoethanesulfonic acid, 60 g of MMA and 38 g of liquefied Bu are added.
Was added over 1 hour under a pressure of 2 MPa, followed by 9
The reaction was performed at 0 ° C. for 3 hours. Next, the mixture was cooled to room temperature for 10 minutes to obtain an aqueous dispersion of Comparative Resin k-2.

Example 3 Preparation of Sheet Materials Samples 301 to 309 A coating liquid prepared so as to have the following coating amount was applied to a 100 μm-thick polyethylene sheet at a coating speed of 200 m / min and dried at 60 ° C. for 1 minute. . Subsequently, heat treatment was performed at 180 ° C. for 1 minute to produce sheet material samples 301 to 309.

Polymer (described in Table 3) 1 g / m ² matting agent (polymethyl methacrylate having an average particle diameter of 3 μm) 0.02 g / m ² Lithium perfluorooctylsulfonamidoethanesulfonic acid 0.01 g / m ² anhydrous Succinic acid 0.03 g / m ²

—Evaluation of Moisture Absorption— The obtained sheet material sample (5 cm × 5 cm) was stored at a relative humidity of 20% for 48 hours, and the moisture content (A) was measured. Thereafter, the same sample was stored for 48 hours at a relative humidity of 80%, the moisture content (B) was measured, and the difference [moisture content (B) -moisture content (A)] (moisture difference) was determined. The moisture content was measured using a Karl Fischer moisture meter MKA-510 manufactured by Kyoto Electronics Industry Co., Ltd.

—Evaluation of Scratch Resistance— 30 μm in diameter installed in a room at 25 ° C. and a relative humidity of 80%
The obtained sheet material sample is passed through a test apparatus in which a slit brush in which 300 nylon fibers each having a length of 20 mm and bundled in a bundle of 300 are set so that a load of 200 g is applied to every fifth pair of opposing rollers is applied. Then, the degree of scratches was examined, and the scratch resistance was evaluated by visual evaluation according to the following evaluation criteria based on the evaluation sample. (Evaluation Criteria) 5: Level without scratches 4: Four to two scratches occurred 3: Five to nine scratches 2: Ten to nineteen scratches 1 : 20 or more scratches are generated Table 3 shows the obtained results.

[0113]

[Table 3]

From the results shown in Table 3, it can be seen that the sheet material coated with the composition containing the polymer composed of the monomer unit represented by the general formula (1) of the present invention has low hygroscopicity and excellent scratch resistance. have.

Example 4 Preparation of Sheet Material Samples 401 to 409 An undercoat coating solution sub-1 prepared so as to have the following coating amount was applied to both sides of a polyethylene terephthalate support having a thickness of 175 μm and dried. Undercoating coating liquid sub-1 polymer (described in Table 4) 0.6 g / m ² silica matting agent (average particle size 1 μm) 0.02 g / m ² Dodecyl sulfonamidoethane sulfonic acid sodium salt 0.02 g / m ²

Subsequently, an undercoating upper layer coating solution sub-2 prepared so as to have the following coating amounts on both surfaces was applied and dried, and heat-treated at 190 ° C. for 1 minute to prepare sheet material samples 401 to 409. Undercoating upper layer coating liquid sub-2 gelatin 0.4 g / m ² silica particles (average particle size 3 μm) 0.1 g / m ² polymer (described in Table 4) 1 × 10 ⁻⁴ mol / m ² 2-hydroxy-1 1,3-bis (vinylsulfonamide) propane 1 × 10 ⁻⁴ mol / m ² dodecylsulfonamide sodium salt 0.015 g / m ² tin oxide doped with 100 ppm indium (average particle diameter 30 nm) 0.14 g / m ² styrene Copolymer of sulfonic acid and maleic acid (molecular weight 200,000) 0.2 g / m ²

—Evaluation of Moisture Absorption— The obtained sheet material sample was evaluated for moisture difference and scratch resistance in the same manner as in Example 3. Table 4 shows the obtained results.

[0118]

[Table 4] From the results in Table 4, the sheet material coated with the composition containing the polymer composed of the monomer unit represented by the general formula (1) of the present invention has low moisture absorption and excellent scratch resistance. ing.

Example 5 The heat-treated sheet material sample 401 prepared in Example 4
To 409 were coated simultaneously with the following photosensitive layer and photosensitive layer protective layer. The coating speed was 236 m / min, the drying temperature was 43 ° C., and the drying time was 48 seconds. As an emulsion,
An emulsion containing silver iodobromide grains having an aspect ratio of 6 (average grain diameter of 2 μm) doped with 100 ppm of indium and rhodium was added with tetraphenylselenourea and chloroauric acid in amounts of selenium and gold atoms per silver halide grain. Emulsions prepared by chemical sensitization by adding each at 134 ppm were used.

Photosensitive layer Emulsion 3 g / m ² (silver content) Sensitizing dye A 1 × 10 ^-5 mol / silver 1 mol

[0121]

Embedded image 1-phenyl-5-mercaptotetrazole 1 × 10 ^-4 mol / silver 1 mol 3-methyl-5-hydroxy-1,3,3a, 7-tetrazaindene 6 × 10 ^-4 mol / silver 1 mol

Photosensitive layer protective layer Gelatin 1 g / m ² Silica matting agent (average particle diameter 3 μm) 0.2 g / m ² Dodecylbenzenesulfonic acid sodium salt 0.023 g / m ^{2 2} -hydroxy-1,3-bis (vinyl) Sulfonamide) propane 0.1 g / m ^{2 On} the side of the support opposite to the side provided with the photosensitive layer and the protective layer, the following back coat (BC) layer and back coat (BC) layer protective layer were provided. The photosensitive material samples 501 to 509 were prepared by multi-layer coating under the same coating conditions and drying conditions as those of the photosensitive layer and the protective layer.

BC layer Gelatin 1.0 g / m ² Dye: f-1 0.2 g / m ²

[0124]

Embedded image Dodecylsulfonamidoethanesulfonic acid sodium salt 0.02 g / m ² Copolymer of sodium styrene sulfonate and maleic acid (molecular weight 250,000) 0.3 g / m ²

BC layer protective layer Gelatin 1.0 g / m ² Polymethyl methacrylate (average particle size 8 μm) 0.2 g / m ²

The photographic performance of the obtained light-sensitive material sample was evaluated. A photosensitive material sample stored for 48 hours at a relative humidity of 20% was exposed and developed using an infrared semiconductor laser of 810 nm with an exposure time of 10 ^-7 seconds while changing the exposure amount, and the sensitivity and fog in normal humidity storage were determined. I asked. Sensitivity is fog +
The density was determined by the reciprocal of the exposure amount at which a density of 0.3 was obtained. Further, the fog was determined by developing an unexposed sample and measuring the density. The developing treatment was carried out using a developing solution and a fixing solution having the following compositions, at a developing temperature of 35 ° C., a developing time of 20 seconds, a fixing temperature of 25 ° C., a fixing time of 13 seconds, and a washing of 20 seconds.

Developer Composition Sodium ethylenediaminetetraacetate 1 g Sodium sulfite 60 g Hydroquinone 20 g 1-Phenyl-3-pyrazolidone 0.5 g Potassium carbonate 38 g Potassium bromide 8 g 5-Methylbenzotriazole 0.5 g Water containing 10% diethylene glycol Add 1 liter. The pH was adjusted to 10.8 with sodium hydroxide.

Fixer composition Ammonium thiosulfate 174 g Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Sodium gluconate 6 g Sulfuric acid 2.4 g Aluminum sulfate 2.2 g Finished to 1 liter with water, pH adjusted to 5.8 with acetic acid Adjust.

Further, the film was sealed in a polyethylene bag having a thickness of 30 μm in an atmosphere of a temperature of 23 ° C. and a humidity of 50%.
Using the photosensitive material sample stored at 8 ° C. for 3 days, the sensitivity and fog under high-humidity storage were determined in the same manner as the sensitivity and fog under normal-humidity storage described above. Table 5 shows the obtained results. The sensitivity under high-humidity storage was shown as a relative sensitivity with the sensitivity under normal-humidity storage at 100.

[0130]

[Table 5] From the results shown in Table 5, it can be seen that the photographic material in which the layer containing silver halide particles was provided on the sheet material of the present invention had good photographic performance preservability.

Example 6 The heat-treated sheet material sample 401 prepared in Example 4
The following antihalation (AH)
An antihalation (AH) layer, a photosensitive layer, an intermediate layer, and a surface protective layer were formed in this order by simultaneous multi-layer coating of a layer, a photosensitive layer, an intermediate layer, and a surface protective layer. The coating speed was 286 m / min, the drying temperature was ° C, and the drying time was 45 seconds.

Antihalation (AH) layer (first layer) Inert gelatin 0.3 g / m ² Dye: f-2 8 mg / m ² Base generator B 13 mg / m ²

[0133]

Embedded image

Photosensitive layer (second layer) Binder: styrene-butadiene (6: 4 mass ratio) copolymer (latex) 4.6 g / m ² Organic silver salt 1.2 g / m ² (silver amount) Sensitization Dye A 1.2 × 10 ^-5 mol / silver 1 mol

[0135]

Embedded image Antifoggants -1: 2-mercaptobenzimidazole 0.3 mg / m ² antifoggant -2: isothiazolone 1.2 mg / m ² antifoggant -3: 2 tribromomethylsulfonylpyridine 120 mg / m ² reducing agent: The pH of the coating solution of 1,1-bis (2-hydroxy-3,5-dimethylphenyl-3,5,5-trimethylhexane 3.3 mmol / m ² photosensitive layer was adjusted to 5.6.

As the organic silver salt, an organic silver salt prepared as follows was used. —Organic silver salt— In 4720 ml of pure water at 80 ° C., 111.4 behenic acid.
g, arachidic acid 83.8 g, stearic acid 54.9 g
Was dissolved. Next, while stirring at a high speed, 540.2 ml of a 1.5 mol aqueous sodium hydroxide solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. While maintaining the temperature of the organic acid sodium solution at 55 ° C., a silver halide emulsion (containing 0.038 mol of silver) and 450 ml of pure water were added, followed by stirring for 5 minutes. next,
760.6 ml of a 1M silver nitrate solution was added over 2 minutes, stirred for another 20 minutes, and the water-soluble salts were removed by filtration. Thereafter, washing and filtration with deionized water were repeated until the conductivity of the filtrate became 2 μS / cm, and water was added to a predetermined concentration to finish the solution. As the silver halide emulsion, silver iodobromide grains doped with 100 ppm of indium and rhodium and having an aspect ratio of 6 (average grain diameter of 42 n
silver halide emulsion prepared by chemical sensitization by adding tetraphenylselenourea and chloroauric acid to the emulsion containing m) so that the addition amounts of selenium and gold atoms per silver halide grain are each 134 ppm. It was used.

Intermediate layer (third layer) Inert gelatin 0.8 g / m ² 5-isopropylphthalazine 0.2 g / m ² 4-methylphthalic acid 0.3 g / m ² Tetrachlorophthalic acid 0.1 g / m ² tetra Chlorophthalic anhydride 0.3 g / m ² Colloidal silica 0.5 g / m ² 1,2- (Bisvinylsulfone acetamide) ethane 0.2 g / m ²

Surface protective layer (fourth layer) Inert gelatin 1.2 g / m ² 4-methylphthalic acid 0.7 g / m ² Tetrachlorophthalic acid 0.2 g / m ² Tetrachlorophthalic anhydride 0.5 g / m ² Silica matting agent (average particle size 5 μm) 0.5 g / m ² 1,2- (bisvinylsulfone acetamide) ethane 0.3 g / m ² Compound of general formula (1): described in Table 4 2 × 10 ⁻⁶ / m ²

Then, the following back coat (BC) layer and back coat (BC) layer protective layer were simultaneously and multi-layer coated on the opposite surface by a curtain coating method to form a back coat (BC) layer and a back coat (BC). 3) Photosensitive material samples 601 to 609 were formed in this order. Was.

Back coat (BC) layer (first layer) Inert gelatin 1.1 g / m ² Dye: f-2 12 mg / m ² Base generator B 10 mg / m ²

[0141]

Embedded image Colloidal silica 12 mg / m ² Sodium dodecylbenzenesulfonate 13 mg / m ² Back coat (BC) layer protective film (second layer) Inert gelatin 0.8 g / m ² Matting agent (PMMA: average particle size 3μ) 0.02 g / m ² activator: N-propyldodecylsulfonamidoacetic acid 0.02 g / m ² Hardener: 1,2-bis (vinylsulfonamido) ethane 0.02 g / m ² Compound of general formula (1): described in Table 5 2 × 10 ^-6 mol / m ²

The photographic performance of the obtained light-sensitive material sample was evaluated. Using the photosensitive material sample stored under the same storage conditions as in Example 5, the sensitivity and fog under normal humidity storage and high humidity storage were determined. However, the photosensitive material sample was processed using a YAG laser (output: 300 mJ / cm ² ). Table 6 shows the obtained results. The sensitivity under high-humidity storage was shown as a relative sensitivity with the sensitivity under normal-humidity storage at 100.

[0143]

[Table 6] From the results shown in Table 6, it can be seen that the photosensitive material in which the layer containing silver halide particles was provided on the sheet material of the present invention had good photographic performance preservability.

Example 7 Example 6 was repeated except that silver halide emulsion A prepared as described below was added to the photosensitive layer (second layer) in an amount of 10% (by mass) of organic silver.
In the same manner as in the above, photosensitive material samples 701 to 709 were produced. —Silver halide grain emulsion A— 7.5 g of inert gelatin and 10 mg of potassium bromide are dissolved in 900 ml of pure water, the temperature is adjusted to 35 ° C. and the pH is adjusted to 3.0, and 370 ml of an aqueous solution containing 74 g of silver nitrate and (9)
An aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 8/2) was added over 10 minutes by a controlled double jet method while maintaining the pAg at 7.7. Then, 4-
0.3 g of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the pH was adjusted to 5 with sodium hydroxide. The silver halide grains of the obtained emulsion had an average grain size of 0.06 μm, the coefficient of variation of the grain size distribution obtained by determining the diameter of a circle having the same area as the projected area of the grains as the grain size, 8%, and the (100) face ratio It was 87% cubic silver iodobromide grains.

This emulsion was subjected to a desalting treatment by flocculating and sedimenting it using a gelatin flocculant. Then, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5. Obtained. And the spectral sensitizing dye A was added 3 × 10- ⁴ mol per mol of silver halide in the silver halide grains.

The photographic performance of the obtained light-sensitive material sample was evaluated. Using the photosensitive material sample stored under the same storage conditions as in Example 5, the sensitivity and fog under normal humidity storage and high humidity storage were determined. However, the photosensitive material sample was exposed with a semiconductor laser sensitometer, preheated at 100 ° C. for 2 seconds using a heat drum (contact with the back coat (BC) side), and further heated at 110 ° C. for 6 seconds. Developed. The semiconductor laser used is a laser that emits light having a wavelength of 810 nm, and the angle between the exposed surface of the photosensitive material sample and the exposed laser light is 80 degrees. Table 7 shows the obtained results. In addition,
Sensitivity in high-humidity storage is 10
The relative sensitivity is shown as 0.

[0147]

[Table 7] From the results shown in Table 7, it can be seen that the photographic material in which the layer containing silver halide particles was provided on the sheet material of the present invention had good photographic performance preservability.

Example 8 Photosensitive material samples 501, 502, 503, 506, 50
8, 601, 602, 603, 604, 606, 60
8, 701, 702, 703, 706, 707, 709
In the production of the photosensitive material samples 801 to 81, the sheet material samples 401 to 409 having the surfaces subjected to corona discharge treatment were used as the sheet material samples.
7 was produced. The conditions of corona discharge treatment are 1 watt to 100 watt / m under atmospheric pressure and argon atmosphere.
・ Selected minutes and implemented. Photosensitive material sample 801 obtained
About 817, evaluation of film attachment was performed.

—Evaluation Method— Evaluation was made by a grid test. 5kP stamps with 5 blades arranged in a grid pattern in a horizontal and vertical direction within 1cm x 1cm
A pressure is applied to the photosensitive material sample with a pressure to make a cut in the film surface,
A cellophane tape was uniformly applied thereon and peeled off after one minute, and the state of film peeling was visually evaluated and evaluated according to the following evaluation criteria. (Evaluation Criteria) 5: Level of no peeling 4: Level of about 10% peeling in area 3: Level of 20% peeling in area 2: 30% peeling in area The evaluation is below the level of 1: 2. Table 8 shows the obtained results.

[0150]

[Table 8] From the results shown in Table 8, it is understood that the film of the sheet material coated with the composition containing the polymer of the present invention is hardly peeled off by the corona discharge treatment.

Example 9 Preparation of Photosensitive Material Samples 901 to 904 In the preparation of the photosensitive material sample 501, a polyethylene terephthalate support having a thickness of 175 μm was used,
A light-sensitive material was prepared in the same manner as the light-sensitive material sample 501 except that a polyethylene terephthalate support of μm was used, and polymers 101, 201, 202, and 203 were used as shown in Table 9 in place of the comparative polymer k-1. Material samples 901 to 90
4 was prepared.

Preparation of Photosensitive Material Samples 905 to 907 In the preparation of the photosensitive material sample 601, a polyethylene terephthalate support having a thickness of 175 μm was used,
A light-sensitive material sample was prepared in the same manner as the light-sensitive material sample 601 except that a polyethylene terephthalate support of μm was used, and polymers 101, 201, and 203 were used as shown in Table 9 in place of the comparative polymer k-1. 905-907 were prepared.

Preparation of Photosensitive Material Samples 908 to 911 In the preparation of the photosensitive material sample 701, a 175 μm thick polyethylene terephthalate support was used,
A photosensitive material was prepared in the same manner as the photosensitive material sample 701 except that a polyethylene terephthalate support of μm was used, and polymers 101, 201, 202, and 203 were used as shown in Table 9 in place of the comparative polymer k-1. Material samples 908-91
1 was prepared. As shown in Table 2, the polymers 201, 202, and 203 have the general formulas (a) to (c) as counter ions.
Having specific examples 1, 4, and 6 of the ions represented by the following formulas:
Was prepared by adding a salt of a counter ion and a chloride ion in an equimolar amount to the carboxylic acid of the polymer 101, and removing chlorine ions to 10 ppm or less in terms of HCl using an anion exchange membrane.

For the photosensitive material samples 901 to 904, the developing time was reduced by 20%, and for the photosensitive material samples 905 to 908, the developing time was reduced by 20%.
Under the conditions shown in Example 6 which were shortened, the photosensitive material sample 90 was used.
For Nos. 9 to 911, development was performed under the conditions shown in Example 7 in which the development time was shortened by 20%. The amount of undeveloped silver in the obtained developed photosensitive material sample was measured. The amount of silver was calculated using a fluorescent X-ray analyzer. Table 9 shows the obtained results.

[0155]

[Table 9] From the results in Table 9, the polymers of the present invention are represented by general formulas (a) to
It can be seen that when a salt is formed with the ion represented by (c), developability can be improved.

Example 10 In the preparation of the sheet material sample 403 of Example 4, the heating temperature and time after coating and drying the upper layer coating solution sub-2 were changed as shown in Table 10. The heat treatment is
A 5 cm × 5 cm sample piece is placed on a heating table in a vacuum-evacuated glass container and heated. Carbon dioxide gas generated during the heat treatment is collected, and the amount of generated gas is measured by a single light source, two light flux non-dispersive infrared absorption method. did. Further, the scratch resistance was evaluated in the same manner as in Example 3. Table 10 shows the obtained results.

[0157]

[Table 10] From the results in Table 10, it can be seen that when the heat treatment is performed at a heat treatment temperature of 80 ° C. to 400 ° C., carbon dioxide is generated, and the scratch resistance is improved.

Example 11 Preparation of Photosensitive Material Sample 1101 A photosensitive material sample was prepared in the same manner as in the preparation of the photosensitive material sample 501 of Example 5, except that gelatin in the protective layer for the photosensitive layer was replaced with an exemplary polymer. 1101 was prepared.

Preparation of Photosensitive Material Samples 1102 to 1104 Photosensitive material sample 1102 was prepared in the same manner as photosensitive material sample 1101 except that sheet material sample 401 was replaced with a sheet material sample shown in Table 11 in preparation of photosensitive material sample 1101.
~ 1104 was prepared.

Preparation of Photosensitive Material Samples 1105 and 1106 In the preparation of the photosensitive material sample 1101, the sheet material sample 401 was changed to the sheet material sample shown in Table 11, and 80% of the gelatin in the protective layer of the photosensitive layer was changed to the exemplified polymer. Photosensitive material sample 1 was prepared in the same manner as photosensitive material sample 1101 except that it was replaced.
105 and 1106 were prepared.

Preparation of Photosensitive Material Samples 1107 to 1109 In the preparation of the photosensitive material sample 1101, the sheet material sample 401 was replaced with the sheet material sample shown in Table 11, and 70% of the gelatin in the protective layer of the photosensitive layer was changed to the exemplified polymer. Photosensitive material sample 1 was prepared in the same manner as photosensitive material sample 1101 except that it was changed.
107-1109 were prepared.

Preparation of Photosensitive Material Sample 1110 In the preparation of the photosensitive material sample 601 of Example 6, an antihalation (AH) layer (first layer) and an intermediate layer (third layer) were prepared.
A light-sensitive material sample 1110 was prepared in the same manner as the light-sensitive material sample 601, except that the inert gelatin for the surface protective layer (fourth layer) and the styrene-butadiene for the light-sensitive layer (second layer) were changed to the exemplified polymer.

Preparation of Photosensitive Material Samples 1111 to 1114 Photosensitive material sample 1111 was prepared in the same manner as photosensitive material sample 1110 except that sheet material sample 401 was replaced with a sheet material sample shown in Table 11 in preparation of photosensitive material sample 1110.
~ 1114 were prepared.

Preparation of Photosensitive Material Samples 1115 and 1116 In the preparation of the photosensitive material sample 1110, the sheet material sample 401 was replaced with the sheet material sample shown in Table 11, and an antihalation (AH) layer (first layer) and an intermediate layer were prepared. (Third
Layer) and a surface protective layer (fourth layer) of inert gelatin,
Photosensitive material samples 1115 and 1116 were prepared in the same manner as in Photosensitive material sample 1110, except that 80% of styrene-butadiene in the photosensitive layer (second layer) was replaced with the exemplified polymer.

Preparation of Photosensitive Material Samples 1117 and 1118 In the preparation of the photosensitive material sample 1110, the sheet material sample 401 was replaced with a sheet material sample shown in Table 11, and an antihalation (AH) layer (first layer) and an intermediate layer were prepared. (Third
Layer) and a surface protective layer (fourth layer) of inert gelatin,
Photosensitive material samples 1115 and 1116 were prepared in the same manner as in Photosensitive material sample 1110, except that 70% of styrene-butadiene in the photosensitive layer (second layer) was replaced with the exemplified polymer.

Preparation of Photosensitive Material Sample 1119 In the preparation of the photosensitive material sample 703 of Example 7, an antihalation (AH) layer (first layer) and an intermediate layer (third layer) were prepared.
A light-sensitive material sample 1119 was prepared in the same manner as the light-sensitive material sample 703, except that the inert gelatin for the surface protective layer (fourth layer) and the styrene-butadiene for the light-sensitive layer (second layer) were changed to the exemplified polymer.

Preparation of Photosensitive Material Samples 1120 and 1211 In the preparation of the photosensitive material sample 1119, except that the sheet material sample 403 was changed to the sheet material sample shown in Table 11, the photosensitive material sample 112 was prepared.
0, 1211 were prepared.

Preparation of Photosensitive Material Samples 1122 and 1123 In the preparation of the photosensitive material sample 1119, the sheet material sample 403 was replaced with the sheet material sample shown in Table 11, and an antihalation (AH) layer (first layer) and an intermediate layer were prepared. (Third
Layer) and a surface protective layer (fourth layer) of inert gelatin,
Photosensitive material samples 1122 and 1123 were prepared in the same manner as in Photosensitive material sample 1119, except that 80% of styrene-butadiene in the photosensitive layer (second layer) was changed to the exemplified polymer.

Preparation of Photosensitive Material Samples 1124 and 1125 In the preparation of the photosensitive material sample 1119, the sheet material sample 403 was replaced with a sheet material sample shown in Table 11, and an antihalation (AH) layer (first layer) and an intermediate layer were prepared. (Third
Layer) and a surface protective layer (fourth layer) of inert gelatin,
Photosensitive material samples 1124 and 1125 were prepared in the same manner as in Photosensitive material sample 1119 except that 70% of styrene-butadiene in the photosensitive layer (second layer) was changed to the exemplified polymer.

Photosensitive Material Samples 1101-1109 Obtained
In the same manner as in Example 5, the sensitivity and fog in storage under normal humidity and storage under high humidity were determined.
In Examples 10 to 1118, the sensitivity and fog in normal humidity storage and high humidity storage were determined in the same manner as in Example 6, and in the photosensitive material samples 1119 to 1125, normal humidity storage and high humidity storage were performed in the same manner as in Example 7. The sensitivity and fog in high-humidity storage were determined. Table 11 shows the obtained results. The sensitivity under high-humidity storage was 100 times the sensitivity under normal-humidity storage.
And relative sensitivity.

[0171]

[Table 11] From the results shown in Table 11, in the photosensitive material, the composition containing the polymer of the present invention contained the photosensitive layer, the antihalation (AH)
It can be seen that the storage stability of the photographic performance is good even if it exists in the layer, the intermediate layer and the surface protective layer.

[0172]

It can be seen that when the polymer of the present invention is used for the photosensitive layer, AH layer and intermediate layer, the storability is improved.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a heat developing device.

[Description of Signs] 1 Heat insulation shield of heat drum 2 Heat roller group 3 Heat source 4 Heat drum 5 Residual heat source 6 Cooling source 7 Residual heat unit 8 Cooling unit 9 Film introduction unit 10 Film discharge unit

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/18 C08J 5/18 7/00 CER 7/00 CER 301 301 302 302 G03C 1/498 501 G03C 1 / 498 501 1/76 351 1/76 351 1/91 1/91 // C08L 101: 00 C08L 101: 00 F term (reference) 2H023 FB02 FB05 2H123 AB00 AB03 AB23 BA00 BA45 BB20 BC00 BC08 BC16 CB00 CB03 4F071 AA04 AA22 AA22X AA30 AA30X AA33 AA33X AA36 AA36X AF10 AH19 BA02 BB02 BC02 4F073 AA01 BA08 BA24 BA26 BB01 CA01 CA21 4J100 AB01Q AB07P AE09P AG01Q AL02Q AL08P AM02Q AN06P AQ11P AQ15P AQ19P AQ28P AS02Q BA02P BA05P BA16P BA17P BA20P BA32P BA33P BA34P BA58P BA59P BC03P BC04P BC33P BC43P BC53P BC69P BC83P CA01 CA03 DA01 JA37

Claims (8)

[Claims] 1. A polymer characterized in that at least a part of the monomer unit is constituted by a monomer unit represented by the general formula (1). Embedded image (Wherein, W ¹ represents a hydrogen atom or an alkyl group, an aromatic group, or a heterocyclic group, each of which may have a substituent;
¹ represents a divalent linking group, and V represents a water-retaining group which is at least partially vaporized by heating and disappears. ) 2. In the general formula (1), at least a part of the water-retaining group represented by V is vaporized by heating and disappears, and at least a part of the water-retaining group disappears by heating to carbon dioxide gas by heating. The polymer according to claim 1, wherein 3. In the general formula (1), the water-retaining group at least a part of which is represented by V and which disappears by gasification by heating is converted into an ion and a salt represented by the general formulas (a) to (c). 3. The polymer according to claim 1, wherein the polymer is a water-retaining group forming Embedded image (In the general formulas (a) to (c), R ^{1 to} R ⁷ each represent a hydrogen atom or an alkyl group, an aromatic group, or a heterocyclic group which may have a substituent, and Z ¹ , Z ² and Z ³ represents a group of atoms necessary to form a 4- to 8-membered ring containing a quaternary nitrogen, and the ring formed by the group of atoms represented by Z ¹ , Z ² and Z ³ represents a substituent. L ¹ represents a divalent linking group, and n represents an integer of 1 to 20.) 4. A sheet material comprising a layer of the composition containing the polymer according to claim 1. 5. The sheet material according to claim 4, wherein the sheet material has been subjected to a corona discharge treatment or a plasma treatment. 6. The sheet material according to claim 4, wherein a layer containing silver halide grains is provided. 7. The sheet material according to claim 4, further comprising a layer containing an organic silver salt. 8. A heat treatment method, wherein the sheet material according to claim 4 is heat-treated at a temperature in the range of 80 ° C. to 400 ° C.