JP2002023298A - Heat developable material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable material which suppresses emission of foul odors during heat developing and saves labor for the maintenance and control of foul odor capturing equipment. SOLUTION: In the heat developing material, containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder on the base, the binder has been subjected to catalytic treatment in the presence of a compound having an active methylene, amino or imino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable material for forming an image by heat development, and more particularly to a heat-developable material which suppresses the odor of a volatile substance or a vaporized substance generated during development of the heat-developable material.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand for photothermographic materials which do not generate waste liquid due to wet processing from the viewpoints of environmental protection and workability in the fields of medical treatment and printing. There is a need for technology relating to photothermographic materials for photographic technology applications that can form images. These photothermographic materials are usually developed at a temperature of 80 ° C. or higher, and are therefore called heat development materials.

Conventionally, this type of heat-developable material has a photosensitive layer containing high-sensitivity silver halide grains spectrally sensitized with a dye, an organic silver salt and a reducing agent, and a light irradiated toward the photosensitive layer. An anti-irradiation layer (AI) for preventing irregular reflection at the interface of the support, intermediate layer, adhesive layer, etc.
Layer) or a backing layer (BC layer), and a protective layer is provided on the photosensitive layer and the BC layer to prevent scratches during handling.

[0004] The binder in each layer of the above-mentioned heat developing material holds various additives and provides a place for appropriately proceeding the oxidation-reduction reaction during heat development. Since even a small amount of water has an adverse effect on preservability, a binder containing as little water as possible is required. Therefore, a styrene-butadiene copolymer or a polyvinyl acetal compound has been applied. However, when such a binder is selected, since unreacted substances of the copolymer monomer and the acetalizing agent slightly remain, they volatilize and evaporate during thermal development, resulting in an odor, and the odor during thermal development processing It will worsen the working environment. In order to prevent the work environment from deteriorating, it is conceivable to reduce unreacted substances in the binder as much as possible, but in order to increase the reaction rate, it is necessary to continue the reaction at a high temperature or for a long time, This is accompanied by reduced production and increased costs. In addition, in order to collect the generated odor, it was necessary to install an adsorption tower filled with an adsorbent and to ventilate the work room. For example, US Pat.
No. 9,238 describes the design of an adsorption tower. These facilities also need to be replaced after the odor has been collected, making maintenance of the equipment difficult.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-developable material which suppresses the generation of odor during the heat development of the heat-developable material and reduces the maintenance of the odor trapping equipment.

[0006]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
This is achieved by the following configurations.

1) photosensitive silver halide grains on a support,
A heat-developable material containing an organic silver salt, a reducing agent and a binder, wherein the binder has been subjected to a contact treatment in the presence of a compound having an active methylene group, an amino group or an imino group. Development material.

2) photosensitive silver halide grains on a support,
A heat development material containing an organic silver salt, a reducing agent and a binder, wherein the binder has been subjected to a contact treatment in the presence of an oxidizing agent.

3) photosensitive silver halide grains on a support,
A heat developing material containing an organic silver salt, a reducing agent and a binder, wherein the binder has been subjected to a contact treatment in the presence of an alkali metal salt.

4) photosensitive silver halide grains on a support,
A heat-developable material containing an organic silver salt, a reducing agent and a binder, wherein the binder has been subjected to a contact treatment in the presence of ultraviolet rays.

5) The heat-developable material as described in 1) above, wherein the compound having an active methylene group, amino group or imino group has a cyclic structure.

(6) The heat developing material as described in (2) above, wherein the oxidizing agent is hydrogen peroxide or ozone.

(7) The heat developing material as described in (3) above, wherein the alkali metal salt is a sodium salt, a potassium salt or a lithium salt.

(8) The heat-developable material as described in (4) above, wherein the ultraviolet ray is 1 μJ to 1 kJ per 1 g of the binder.

9) The heat-developable material as described in any one of 1) to 8) above, wherein the binder is a copolymer of butadiene and styrene or a polyvinyl acetal compound.

10) The temperature at which the binder is treated is -20 to 2
The heat-developable material according to any one of 1) to 8) above, wherein the heat-developable material has a temperature of 00 ° C and a pressure of 10 kPa to 40 MPa.

Hereinafter, the present invention will be described in detail. The heat-developable material of the present invention usually comprises at least one photosensitive layer on a support and at least two layers comprising a layer adjacent to the photosensitive layer, and a BC layer on the opposite side of the photosensitive layer. And a protective layer thereof. The photosensitive layer of the heat-developable material contains photosensitive silver halide grains which may be sensitized with a spectral sensitizing dye, and the photosensitive layer or a layer adjacent to the photosensitive layer contains an organic silver salt serving as a silver source, silver. A reducing agent is included for developing the salt to form a silver image.

The photosensitive silver halide contained in the photosensitive layer of the heat-developable material of the present invention can be prepared by any method known in the field of photographic technology such as a single jet method or a double jet method, for example, in an ammonia emulsion. It can be prepared in advance by any method such as a sexual method and an acidic method, and then mixed with other components of the present invention and introduced into the composition used in the present invention. The photosensitive silver halide preferably has a small grain size in order to suppress white turbidity after image formation and to obtain good image quality. 0.1μ in average particle size
m, preferably 0.01 to 0.1 μm, particularly 0.0
2 to 0.08 μm is preferred. The shape of the silver halide is not particularly limited, and may be cubic, octahedral, so-called normal crystals, or non-normal crystals, such as spherical, rod-shaped, or tabular grains. The silver halide composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. The amount of the silver halide is 50% by mass or less, preferably 25 to 0.1% by mass, more preferably 15 to 15% by mass based on the total amount of the silver halide and the organic silver salt described below.
0.1% by mass.

The photosensitive silver halide prepared by the above-mentioned various methods includes, for example, sulfur-containing compounds, gold compounds,
Platinum compounds, palladium compounds, silver compounds, tin compounds,
Chemical sensitization can be performed by a chromium compound or a combination thereof. The method and procedure of the chemical sensitization are described in, for example, U.S. Pat. No. 4,036,650, British Patent 1,518,850, and JP-A-51-22430.
And Nos. 51-78319 and 51-81124.

In addition, these photosensitive silver halides may include one or more of the elements in Group 6 of the periodic table for the purpose of illuminance failure and gradation adjustment.
Metals belonging to Group 0, such as Rh, Ru, Re, Ir, O
An ion such as s or Fe, a complex thereof or a complex ion can be contained. It is particularly preferable to contain ions or complex ions of metals belonging to Groups 6 to 10 of the periodic table. As the above metals, W, Fe, Co, Ni,
Cu, Ru, Rh, Pd, Re, Os, Ir, Pt, A
u is preferable, and when it is 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.

The content of metal ions or complex ions is generally 1 × 10 ^-9 per mol of silver halide.
~ 1 × 10 ^-2 mol is suitable, preferably 1 × 10 ^-8 mol.
１1 × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening May be added at any stage before and after chemical sensitization, but it is particularly preferred to add at the stage of nucleation, growth and physical ripening.

The organic silver salt contained in the heat-developable material of the present invention is a reducible silver source, and organic acids, heteroorganic acids, and silver salts of acid polymers containing a reducible silver ion source are used. . Also useful are organic or inorganic silver salt complexes in which the ligand has a total stability constant for silver ions of 4.0 to 10.0. An example of a silver salt is Research Di.
and the salts thereof are described in, for example, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, arachidic acid, erucic acid, and the like.

Examples of preferred reducing agents contained in the heat-developable material of the present invention are described in US Pat. Nos. 3,770,448, 3,773,512, 3,593,863 and R.
D Nos. 17029 and 29963, and include the following.

Bisphenols such as bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol (m
esitol), 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-methylphenol), and particularly preferred reducing agents are hindered bisphenols. The hindered bisphenols include the compounds shown below.

[0025]

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The compounds shown above are used by dispersing in water or dissolving in an organic solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene and xylene can be arbitrarily selected. The amount of the reducing agent used is 1 × 10 ^-2 to 10 mol, preferably 1 × 10 ^{-2 to} 1.5 mol, per 1 mol of silver.

As the binder used for the photosensitive layer or the non-photosensitive layer of the heat-developable material of the present invention, a material which is preferable as a place where silver halide, organic silver salt and reducing agent react is selected. Examples of the binder include polymers used by dissolving in polar solvents including alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, dimethyl sulfoxide and dimethylformamide, and water-dispersed polymers.

Examples of the polymer include cellulose acetate butyrate, cellulose derivatives such as cellulose acetate and cellulose butyrate, polyvinyl butyral, polyvinyl acetal, and the like, which are used by being dissolved in an organic solvent.
There are polyvinyl alcohol derivatives such as polyvinyl hexanal, which are used by dispersing or dissolving in water.
Polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, sodium polyacrylate, polyethylene oxide, acrylamide-acrylate copolymer, styrene-maleic anhydride copolymer, polyacrylamide, sodium alginate, gelatin,
Casein, polystyrene, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, styrene-butadiene-acryl copolymer And the like.

The compound having an active methylene group for treating the binder is a group having at least one electron-withdrawing group in a group adjacent to the methylene group, and it is particularly preferable that there is an electron-withdrawing group on both sides. As the electron withdrawing group, a carbonyl group,
Examples include a cyano group, a sulfonyl group, a nitro group, a halogen atom (such as a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom), and an ester group (such as a carbamoyl group and an acetyl group), and a carbonyl group is particularly preferable. The compound may be linear or branched, but preferably has a cyclic structure and an active methylene group in the ring.

The compound having an amino group or an imino group may be a linear or branched compound, but preferably has a cyclic structure. As these rings, saturated or unsaturated rings such as aromatic rings and hetero rings can be selected. Specific examples of preferred rings include a benzene ring, a naphthalene ring, an adamantane ring, an oxazole ring, an isoxazole ring, an imidazole ring, a thiazole ring, a triazole ring, a tetrazole ring, a purine ring, a triazine ring, a pyrazolone ring, a benzimidazole ring, and benzo. A triazole ring, a benzothiazole ring, a benzoxazole ring, a cyclohexane ring, a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a pyridone ring, and the like. The amino group is preferably bonded directly to the above ring, and may be bonded via a linking group. The ring may have not only one but a plurality of amino groups.

Specific examples of the compounds having an active methylene group, amino group or imino group are shown in the following table.

[0032]

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[0033]

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[0034]

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[0035]

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The above compounds can be chemically or strongly bound to the binder by treating with the binder. A strong bond is introduced by a covalent bond, while a weak bond can be bonded as an ionic bond or a ligand, for example, by an unpaired electron of an amino group or an imino group.

Specifically, the binder is dispersed in water or dissolved in an organic solvent such as a ketone or an alcohol, and then the temperature is lowered.
20 ° C. to 200 ° C., the pressure is controlled between 10 kPa to 40 MPa, and the active methylene group, the amino group,
Dispersing or dissolving a compound having an imino group in water,
The mixture is treated with a solution containing a binder. The mixing ratio of treating the compound of the present invention with the binder is preferably 1/2 to 1,000,000 per binder. Particularly preferably, it is 1/10 to 1 / 10,000. After treating the binder, the treated binder may be dissolved in water or an organic solvent and re-purified, or may be used as it is. Purification may be carried out by coagulation precipitation or by using an adsorbent such as activated carbon, silica gel or zeolite.

The oxidizing agent of the present invention is a compound capable of oxidizing a monomer or a polymerization degree controlling agent used for forming a polymer, or an aldehyde or ketone used for cross-linking of a polymer, which is reduced by itself. , Ozone, hydrogen peroxide, peroxide, copper oxide, silver oxide, cerium oxide, chloric acid, hypochlorous acid, and organic peroxide. Of these compounds, those which are produced when they are reduced, are preferably photographically inactive. In particular, ozone and hydrogen peroxide are preferred oxidizing agents in the present invention because they become oxygen and water after decomposition. Benzoyl peroxide (BPO), azobisbityronitrile (AI
BN), sodium persulfate (KPS), ammonium persulfate (KPA), acetyl peroxide (APO), potassium peroxide, sodium hydrogen peroxide, lauroyl peroxide (L
PO), di-tert-butyl peroxide (DT)
BPO), cumene hydroperoiside (CHPO)
And the like.

The oxidizing agent is preferably used after dissolving the binder in water or an organic solvent, in an amount of 10 ppb to 30%, more preferably 10 ppm to 30% based on the weight of the binder.
20%. The temperature for processing this is -20 to 200
C., the pressure is 10 kPa to 40 MPa, and the treatment is preferably performed at 100 ° C. or more and within 10 minutes. The peroxide is
If the reaction temperature is high, some explode, so -20 to 20
It is preferable to control the temperature in the range of ° C. and to carry out the treatment under a slow reaction condition at a low temperature for a long time.

In the alkali metal salt treatment, a salt of an alkali metal selected from sodium, potassium and lithium with a hydroxide ion, a carbonate ion, a bicarbonate ion, a sulfite ion, a phosphate ion, an organic carboxylate ion and an organic sulfonate ion is formed. preferable. Particularly, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are preferable.

The ultraviolet light used in the present invention is 100 to 40.
Ultraviolet rays having a wavelength of 0 nm may be a bright line spectrum or a broad type. The ultraviolet ray generating tube includes a xenon lamp, a low-pressure or high-pressure mercury lamp, or the like. The intensity of the ultraviolet light can be arbitrarily selected from 1 μW to 1 MW.
As a method of irradiating the binder with ultraviolet rays, the powder may be irradiated, or a solution dissolved or dispersed in water may be irradiated.
When irradiating the binder, a method of irradiating the particles while dropping them in a cyclone, a fluidized bed irradiation of irradiating particles floated by applying wind pressure from below, or the like, or irradiating by arranging the powder on a shelf May be used. When irradiating with a liquid, a method in which a liquid dissolved or dispersed in water is allowed to flow down around a tube that generates ultraviolet rays to irradiate the liquid, the liquid is allowed to flow down like a waterfall from the slide die surface, and is applied to the slide surface or the lower surface of the flow. There is a method of irradiating ultraviolet rays and the like. In the present invention, irradiation is performed at 1 μJ to 1 kJ per gram mass of the binder. If it is smaller than 1 μJ, the effect of the present invention is hardly obtained,
If it is larger than 1 kJ, the photographic performance is adversely affected by the decomposition of the binder by ultraviolet rays. The temperature at which the binder is treated is between -20 and 200C, preferably between 10 and 200C. If the temperature exceeds 200 ° C., the treatment can be performed in a very short time to avoid damaging the binder, but it is preferable to avoid the damage because energy loss is increased. The pressure is 10 kPa to 40 MPa, and 100 kPa
The range of Pa to 40 MPa is preferable. Pressures higher than this are preferred to be avoided because of the increased energy loss. In the range of 1 MPa to 20 MPa, the treatment can be completed within 0.001 second to 10 seconds, so that it is suitable for a continuous flow reactor treatment method.

The spectral sensitizing dye according to the present invention may be used, if necessary, for example, as described in JP-A-63-159814 and JP-A-60-14.
No. 0335, No. 63-231437, No. 63-259
No. 651, No. 63-304242, No. 63-1524
5, U.S. Pat. Nos. 4,639,414 and 4,741;
No. 0,455, No. 4,741,966, No. 4,7
Sensitizing dyes described in JP-A Nos. 51,175 and 4,835,096 can be used.

Useful sensitizing dyes according to the present invention include, for example, RD 17643 IV-A (p.2, December 1978, p.2).
3), and the literature described or cited in section 1831X (p. 437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-80
No. 679 is preferably used.

The heat-developable material of the present invention is provided with an AI layer or a BC layer for preventing irradiation or halation of the heat-developable material, if necessary. Any dye can be used as long as it absorbs light.
The heat-decolorable dye described in US Pat. No. 4,237 is used.
If the dye used is not heat-decolorable, the amount used is limited to a range that does not cause image damage to the heat-developable material. If the heat-decolorable dye is used, a necessary and sufficient amount of the dye is added. be able to.

It is preferable to add a toning agent to the heat-developable material of the present invention. An example of a suitable toning agent is RD17029
And includes the following:

Phthalazinone, phthalazinone derivatives or metal salts of these derivatives (for example, 4- (1-naphthyl)
Phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone), quinazolinedione, benzoxazine or naphthoxazine derivative, benzoxazine-2,4-dione (eg, 1,3-benzoxazine-2) , 4-dione), pyrimidines and asymmetric-
Triazines (eg, 2,4-dihydroxypyrimidine).

In the present invention, silica or polymethyl methacrylate is used as a matting agent. The shape of the matting agent may be either regular or irregular, but preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere.
The particle size of the matting agent indicates the diameter converted into a sphere. The matting agent has an average particle size of 0.5 to 10 μm
And more preferably 1.0 to 8.0.
μm. The method of adding the matting agent may be a method in which the matting agent is dispersed in a coating solution in advance, or a method in which the matting agent is sprayed before the drying is completed after the coating solution is applied. When a plurality of types of matting agents are added, both methods may be used in combination.

As the support, supports such as paper, synthetic paper, non-woven fabric, metal foil, plastic films such as polyethylene terephthalate and polyethylene naphthalate can be used, and a composite sheet obtained by combining these can be used arbitrarily. Is also good.

The image exposure for forming an image on the heat-developable material of the present invention is performed, for example, at an emission wavelength of 660 nm or 670 nm.
m, 780 nm, 810 nm, or 830 nm, which is preferably performed by laser scanning exposure. However, a laser scanning exposure machine is used in which the angle between the exposed surface of the heat-developable material and the scanning laser beam is not substantially perpendicular. Is preferred. Here, "not substantially vertical" means that the laser scanning angle is preferably 55 to 88 degrees, more preferably 60 to 86 degrees, still more preferably 65 to 84 degrees, and most preferably 70 to 82 degrees. It means that. The beam spot diameter on the exposed surface of the photothermographic material when the laser beam is scanned on the photothermographic 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 related to reflected light such as occurrence of unevenness like interference fringes.

The exposure in the present invention is also preferably performed by using a laser scanning exposure machine which emits a scanning laser beam which is a vertical multi. By using vertical multi-mode laser exposure, image quality deterioration such as occurrence of interference fringe-like unevenness is reduced as compared with vertical single-mode scanning laser light. In addition to the above-described method, there is a method of using the multiplexing method, utilizing the return light, and applying high-frequency superimposition. In addition, the vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5 nm or more, preferably 10 nm or more.
nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.

[0051]

EXAMPLES Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Subbed Support> A polyethylene terephthalate support having a thickness of 175 μm was subjected to a corona discharge treatment of 8 W / m ² · min on both sides, and the following coating solution a- 1 was applied and dried to the following amount to provide an undercoat layer A-1, and the following undercoat coating solution b-1 was applied to the opposite surface to the following amount and dried. To provide an undercoat layer B-1.

<< Undercoating Coating Solution a-1 >> Copolymer of butyl acrylate (30% by mass), t-butyl acrylate (20% by mass) styrene (25% by mass), 2-hydroxyethyl acrylate (25% by mass) Latex liquid (solid content 30%) 800 mg / m ² Phenylaminopropyltrimethoxysilane 20 mg / m ² << Undercoating solution b-1 >> Butyl acrylate (40% by mass), styrene (20% by mass), glycidyl acrylate ( 40% by mass) copolymer latex liquid (solid content 30%) 400 mg / m ² Phenylaminopropyltrimethoxysilane 20 mg / m ² Subsequently, on the upper surfaces of the undercoat layer A-1 and the undercoat layer B-1,
A corona discharge of 8 W / m ² · min is applied, and the following undercoating layer A-1 is coated and dried on the undercoating layer A-1 so that the following coating amount a-2 is applied to the undercoating layer A-1. Was formed on the undercoat layer B-1 by applying and drying the following undercoating layer coating solution b-2 in the following amounts to form an undercoating upper layer B-2 having an antistatic function.

<< Lower Coating Upper Layer Coating Solution a-2 >> Polyvinyl Butyral 0.4 g / m ² Silica Particles (Average Particle Size 3 μm) 100 mg / m ² << Lower Coating Upper Layer Coating Solution b-2 >> Styrene butadiene copolymer latex liquid ( 200 nm / m ² Tin oxide fine particles (average particle diameter 20 nm) 200 mg / m ² <Preparation of silver halide grain emulsion A> 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water. After adjusting the temperature to 35 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (98/2) were pAg
It was added over 10 minutes by the controlled double jet method while maintaining at 7.7. Then 4-hydroxy-6
0.3 g of methyl-1,3,3a, 7-tetrazaindene
Was added, and the pH was adjusted to 5 with NaOH. The average particle size was 0.06 μm, the variation coefficient of the projected diameter area was 8%, and [1
00] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, and then 0.1 g of phenoxyethanol was added to obtain 321 g of silver halide grain emulsion A.

<Preparation of Organic Silver Salt> 111.4 g of behenic acid, 83.8 g of arachidic acid and 54.9 g of stearic acid were dissolved in 4720 ml of pure water at 80 ° C. Next, while stirring at a high speed, a 1.5 mol aqueous sodium hydroxide solution 54
0.2 ml was added (pH 9.8) and 6.9 ml of concentrated nitric acid was added.
Was added (pH 9.3), and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. While maintaining the temperature of the above organic acid sodium acid solution at 55 ° C., the silver halide grain emulsion A
(Containing 0.038 mol of silver) and 450 ml of pure water were added and stirred for 5 minutes. Next, 1 mol of silver nitrate solution 760.6 m
was added over 2 minutes, stirred for another 20 minutes, and the water-soluble salts were removed by filtration. Then, the conductivity of the filtrate was 2
Washing with deionized water and filtration were repeated until the solution reached μS / cm, and finally, centrifugal separation and dehydration were followed by drying at 40 ° C. for 15 minutes.

<Treatment of Binder> A sample was prepared by sequentially forming the following layers on the support provided with the undercoat layer. Table 1
In the above, since the same sample used the same composition of the binder, the layer in which the binder was used was omitted. The polyvinyl butyral used was one obtained by saponifying 98% of vinyl acetate and performing butyralization of the hydroxyl group with butyraldehyde to 86 mol% (hereinafter abbreviated as PVB-1). The styrene-butadiene copolymer used had a molar ratio of styrene to butadiene of 1: 3 and was emulsified in water with an average particle diameter of 100 nm (hereinafter abbreviated as SB-1). When polyvinyl butyral is used, it is dissolved in a methyl ethyl ketone solution to a solid content of 30% by mass,
The amino compound of the present invention in this solution while heating to
An imino compound or an active methylene compound was added at 1% by mass based on the mass of polyvinyl butyral, and reacted for 6 hours to obtain a dispersion. When a styrene-butadiene copolymer is used, 1% by mass of the amino compound, imino compound or active methylene compound of the present invention in an aqueous dispersion having a solid content of 38% by mass is based on the mass of the styrene-butadiene copolymer. Was selected from specific compounds and treated at 90 ° C. for 6 hours. A coating solution using polyvinyl butyral was prepared in a methyl ethyl ketone solution, and a coating solution using a styrene-butadiene copolymer was prepared in an aqueous system. Each sample was dried at 45 ° C. for 1 minute.

<Coating on the BC Layer> On the back surface side, a coating solution prepared by adding the following additives was applied and dried in the following amounts to form a BC layer.

<< Coating of BC Layer >> Content of Binder Described in Table 1 1.8 g / m ² C1 1.2 × 10 ⁻⁵ mol / m ² Activator: Perfluorooctylsulfonic acid 0.02 g / m ² Dihexyl sulfosuccinic acid sodium salt 0.02 g / m ² phenyl aminopropyltrimethoxysilane 0.02 g / m ² "BC protective layer coating" gelatin 1.1 g / m ² 1,2-bis (vinyl scan Hong amide) ethane 0.01 g / m ² N-propyl perfluorooctylsulfonamidoacetic acid 0.02 g / m ² matting agent (PMMA: average particle size 5 μm) 0.12 g / m ² <Coating on photosensitive layer side><< Application of AI layer >> Binder content described in Table 1 0 0.4 g / m ² C1 1 × 10 ⁻⁵ mol / m ² << Coating of photosensitive layer >> To form a photosensitive layer, methyl ethyl ketone was added to the following composition to prepare a coating solution. This coating solution was kept at about 35 ° C., and was applied and dried so as to have the following amount. The organic silver salt was added in such an amount that the silver amount became 1.4 g / m ² .

[0059] The binder content shown in Table 1 2.6 g / m ² sensitizing dye A1 2 × 10 ^-5 mol / m ² antifoggant -1: pyridinium hydrobromide perbromide 0.3 mg / m ² antifoggant - 2: isothiazolone 1.2 mg / m ² tribromomethylsulfonyl quinoline 20 mg / m ² reducing agent 4 3.3 mmol / m ²

[0060]

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<< Coating of Photosensitive Layer Protective Layer >> A coating solution prepared by adding the following composition was applied on the photosensitive layer so as to have the following coating amount and dried to form a photosensitive layer protective layer.

Cellulose acetate butyrate 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 0.5 g / m ² Phenylpropyltrimethoxysilane 0.3 g / m ² <Evaluation of photographic performance> The sample prepared above was divided into two parts, and one of them was placed at 25 ° C. in an atmosphere of 45% RH for 3 days. After preservation, it is exposed with a 810 nm semiconductor laser exposure sensitometer, and is contacted with a heat developing device (contact with a heat drum on the BC side) 120.
Heated at <RTIgt; 8 C </ RTI> for 8 seconds.

The sensitivity and fog of the sample were measured with a densitometer. The sensitivity was evaluated by the reciprocal of the ratio of the exposure amount giving a density 0.3 higher than the fog density, and the sample 101 was used as a reference (1
00) by relative evaluation.

<Evaluation of Odor> For the evaluation of odor, air was drawn out of the shielded heat development section, and the degree of odor was measured with an odor sensor. The sensor is made of a semiconductor and can be detected by a change in electric conductivity when an odorous substance is adsorbed.
The odor intensity is diluted twice, and when the odor is no longer felt after dilution n times, the odor intensity is evaluated as n. The sensor values were set so as to show values of 400 for odor intensity 2, 800 for odor intensity 3, 1600 for odor intensity 4, and 3200 for odor intensity 5.

[0065]

[Table 1]

From Table 1, it can be seen that the use of the compound of the present invention does not cause an increase in fog or a decrease in sensitivity and can suppress the odor level. In particular, the compounds of the present invention are preferably cyclic amino compounds and imino compounds.

Example 2 A sample was prepared in the same manner as in Experiment No. 101 (using an untreated binder) of Example 1, except that the binder used was PVB.
1 liter of a 30% (solid content mass%) methyl ethyl ketone solution was prepared, and 30 ml of a 3% oxidizing agent (hydrogen peroxide solution or organic peroxide) was added to the solution. 100 ml of air containing 1000 ppm was introduced, and the temperature and pressure were changed as shown in Table 2 below. A sample was prepared using the oxidized PVB-1, and photographic performance and odor were measured in the same manner as in Example 1. In the case of a styrene-butadiene copolymer, it was added or introduced into an emulsified aqueous solution containing 30% by mass of SB-1. The results obtained are shown in Table 2 below.

[0068]

[Table 2]

From Table 2, it can be seen that oxidizing the binder at the temperature and pressure of the present invention does not cause an increase in fog or a decrease in sensitivity, and can suppress the odor level.

Example 3 A sample was prepared in the same manner as in Experiment No. 101 of Example 1,
The binder was treated with an alkali metal salt. 300 g of the binder was dispersed in 1 L of water, and the mixture was treated by adding an alkali metal salt as shown in Table 3 below. Using an ultrahigh pressure jet disperser, the dispersed particle size of the binder in the liquid was 1 μm or less. The dispersion was allowed to settle by standing, and then dehydrated and dried. Using this binder, a sample was prepared in the same manner as in Experiment No. 101 of Example 1,
The photographic performance and odor were evaluated in the same manner as in Example 1.

[0071]

[Table 3]

It can be seen that treating the binder with an alkali metal salt improves the odor. Example 4 A sample was prepared and its performance was evaluated in the same manner as in Experiment No. 101 of Example 1, except that the binder was treated with ultraviolet light. Ultraviolet light is applied to an aqueous dispersion with a solid content of 30% by mass using a high-pressure mercury lamp (output 5k).
W) was placed in a cylindrical tube in which it was placed, and irradiated to the amount shown in Table 4. Irradiation was performed on two glass plates with a thickness of 10 mm.
It flowed down to the slit gap of 00 μm, and the glass surface was irradiated with ultraviolet rays. The irradiation amount was calculated using an integrating photometer as the amount of irradiation per 1 gram mass of the solid content of the binder.
Table 4 shows the obtained results.

[0073]

[Table 4]

It can be seen that the odor is improved by treating the binder with ultraviolet light.

[0075]

According to the present invention, the odor volatilized when the heat-developable material is thermally developed can be reduced without affecting the photographic performance such as fog and sensitivity.

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Claims (10)

[Claims] 1. A heat-developable material containing a photosensitive silver halide particle, an organic silver salt, a reducing agent and a binder on a support, wherein the binder has an active methylene group, an amino group or an imino group. A heat-developable material which has been subjected to a contact treatment in the presence. 2. A heat-developable material containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder on a support, wherein the binder has been subjected to a contact treatment in the presence of an oxidizing agent. A heat-developable material, characterized in that: 3. A heat-developable material containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder on a support, wherein the binder has been contact-treated in the presence of an alkali metal salt. A heat-developable material characterized by the following. 4. A heat-developable material containing photosensitive silver halide grains, an organic silver salt, a reducing agent and a binder on a support, wherein the binder has been subjected to contact treatment in the presence of ultraviolet rays. A heat development material characterized by the following. 5. The heat developing material according to claim 1, wherein the compound having an active methylene group, amino group or imino group has a cyclic structure. 6. The heat-developable material according to claim 2, wherein the oxidizing agent is hydrogen peroxide or ozone. 7. The method according to claim 3, wherein the alkali metal salt is a sodium salt, a potassium salt or a lithium salt.
2. The heat-developable material according to item 1. 8. The method according to claim 1, wherein the ultraviolet light is applied at a rate of 1 to 1 gram of the binder.
The heat development material according to claim 4, wherein the heat development material has a μJ of 1 kJ. 9. The heat developing material according to claim 1, wherein the binder is a copolymer of butadiene and styrene or a polyvinyl acetal compound. 10. The temperature for treating the binder is -20 to 20.
The heat developing material according to any one of claims 1 to 8, wherein the temperature is 0 ° C and the pressure is 10 kPa to 40 MPa.