JP2001183771A - Heat developable photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photographic sensitive material with subbing layers which retain excellent adhesiveness even when heated. SOLUTION: In the head developable photographic sensitive material with at least two subbing layers on at least one face of the polyester support, the elastic modulus of the lowest subbing layer is >=1×109 N/m2 and that of the top subbing layer is <1×109 N/m2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material and more particularly to a photothermographic material having an undercoat layer having good adhesion.

[0002]

2. Description of the Related Art In recent social situations that require consideration for the environment, ordinary silver halide photographic light-sensitive materials subjected to wet development processing have reached the present level while overcoming problems such as waste liquid. For example, the problem has been solved by reducing the amount of replenisher so as to minimize wastewater, solidifying the chemical, and recycling the treatment liquid. Under such an environment, a non-wet dry silver halide photographic material has been developed. For example, a heat-developable photographic material called dry silver, which is composed of silver halide, a reducing agent, silver fatty acid, etc., does not use any water and has no waste. It is about to be used in business areas.

[0003] Such a heat-developable photographic light-sensitive material has a
This is an environmentally friendly silver halide photographic light-sensitive material that is developed by applying heat of 0 to 150 ° C. and requires almost no subsequent processing. However, after heat development, the support and the silver halide emulsion layer often peel off, which has been an important issue in developing heat-developable photographic materials. In particular, as a heat-resistant support is used, such a phenomenon has become more likely to occur.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photothermographic material having an undercoat layer having excellent adhesion even when heated.

[0005]

The above objects of the present invention have been attained by the following constitutions.

(1) In a photothermographic material having at least one undercoat layer on at least one surface of a polyester support, the lowermost undercoat layer has an elastic modulus of 1 × 10
⁹ N / m ² or more, and the elastic modulus of the undercoating uppermost layer is 1 ×
A heat-developable photographic light-sensitive material, characterized by having a density of less than 10 ⁹ N / m ² .

(2) A photothermographic material having at least one undercoat layer on at least one surface of a polyester support, wherein the lowermost undercoat layer contains a filler. .

(3) A heat-developable photographic material having at least one undercoat layer on at least one surface of a polyester support, wherein the lowermost undercoat layer contains a conductive metal oxide. Developed photographic photosensitive material.

(4) In a photothermographic material having at least two undercoat layers on at least one surface of a polyester support, an undercoat uppermost layer is provided adjacent to and above the undercoat uppermost layer. A photothermographic material comprising at least 5% by mass or more of a binder constituting a layer.

(5) In a photothermographic material having at least two subbing layers on at least one surface of a polyester support, the subbing uppermost layer is coated adjacent to the subbing uppermost layer. A photothermographic material which swells or dissolves in a solvent of a coating solution.

(6) In a photothermographic material having at least one undercoat layer on at least one surface of a polyester support, the binder constituting the undercoat uppermost layer is adjacent to the uppermost undercoating layer. A heat-developable photographic light-sensitive material, which is compatible with a binder constituting a layer to be coated.

(7) In a photothermographic material having an undercoat layer on at least one surface of a polyester support, at least one of the undercoat layers contains a hydrophilic binder as a main component and has a dry film thickness of at least 0.1. A heat-developable photographic light-sensitive material having a thickness of not more than 05 μm.

(8) In a photothermographic material having an undercoat layer on at least one surface of a polyester support, at least one of the undercoat layers contains at least two kinds of acrylic polymer latex and an epoxy group-containing crosslinking agent. And the glass transition temperature (TgH) of the acrylic polymer latex exhibiting the lowest glass transition temperature and the glass transition temperature (TgH) of the acrylic polymer latex exhibiting the highest glass transition temperature. A photothermographic material, wherein the difference is from 10 to 80C.

(9) In a photothermographic material having an undercoat layer on at least one surface of a polyester support, at least one of the undercoat layers contains at least two kinds of acrylic polymer latex and an oxazoline group-containing crosslinking agent. And the glass transition temperature (TgH) of the acrylic polymer latex exhibiting the lowest glass transition temperature and the glass transition temperature (TgH) of the acrylic polymer latex exhibiting the highest glass transition temperature. A photothermographic material, wherein the difference is from 10 to 80C.

Hereinafter, the present invention will be described in more detail. The polyester of the polyester support used in the present invention is a polymer obtained by condensation polymerization from a diol and a dicarboxylic acid, and as the dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, The diol is represented by sebacic acid and the like, and the diol is represented by ethylene glycol, trimethylene glycol, tetramethylene glycol, cyclohexanedimethanol and the like. Specifically, for example, polyethylene terephthalate, polyethylene-p-oxybenzoate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,
6-naphthalenedicarboxylate and the like can be mentioned. In the case of the present invention, polyethylene terephthalate and polyethylene naphthalate are particularly preferred. The polyethylene terephthalate film is excellent in water resistance, durability, chemical resistance and the like.

Of course, these polyesters may be homopolyesters or copolyesters. As the copolymerization component, diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and adipic acid, sebacic acid, phthalic acid,
Examples thereof include dicarboxylic acid components such as 6-naphthalenedicarboxylic acid and 5-sodium sulfoisophthalic acid.

In the present invention, fine particles such as calcium carbonate, amorphous zeolite particles, anatase type titanium dioxide, calcium phosphate, silica, kaolin, talc and clay may be used in combination with the polyester support. The amount of these additives is preferably 0.0005 to 25 parts by mass based on 100 parts by mass of the polyester composition. In addition to such fine particles, fine particles precipitated by the reaction between a catalyst residue and a phosphorus compound in a polyester polycondensation reaction system can be used in combination. Examples of the precipitated fine particles include those composed of calcium, lithium and phosphorus compounds, and those composed of calcium, magnesium and phosphorus compounds. The content of these particles in the polyester is 0.0
It is preferably from 5 to 1.0 part by mass.

Further, various known additives such as an antioxidant and a dye may be added to the polyester support.

The thickness of the polyester support is 10
It is preferably from 250 to 250 μm. More preferably, the thickness is 15 to 150 μm. If the thickness is smaller than this, the mechanical strength of the film is insufficient, and if the thickness is larger than this, the running property deteriorates, which is not preferable.

As described in JP-A-51-16358, the polyester support is formed after forming the polyester support into a film in a temperature range equal to or lower than the glass transition temperature in order to reduce curl. 0.1-1500
Heat treatment for a long time may be performed to reduce curling.

The polyester support may be subjected to a known surface treatment or chemical treatment (for example, JP-B Nos. 34-11031, 38-22148, and 40) in order to improve the adhesiveness, if necessary.
No.-2276, No.41-16423, No.44-511
No. 6), chemical mechanical surface roughening treatment (Japanese Patent Publication No. 477-1)
Nos. 9068 and 55-5104), corona discharge treatment (Japanese Patent Publication No. 39-12838, Japanese Patent Application Laid-Open No. 47-1982)
4, JP-A-48-28067), fire treatment (JP-B-40-12384, JP-A-48-85126), ultraviolet treatment (JP-B-36-18915, JP-B-37-187)
No. 144493, No. 43-2603, No. 43-260
4, No. 52-25726), high-frequency treatment (described in JP-B-49-10687), glow discharge (described in JP-B-37-107)
-17682 description), further, active plasma treatment,
Laser treatment or the like may be performed. As described in JP-B-57-487, it is preferred that the contact angle between the surface of the support and water is 58 ° or less by these treatments.

The polyester support may be transparent, opaque, or colored.

The binder used for the undercoat layer of the present invention can be used without any limitation as long as it is a resin for an undercoat layer used in the art. For example, acrylic acid or acrylic acid esters (including methacrylic acid or methacrylic acid esters), vinyl esters, vinyl ketones,
Styrenes, diolefins, acrylamides (including methacrylamides), vinyl chlorides (including vinylidene chlorides), monomers having active methylene (for example, see US Pat. No. 4,215,195). A hydrophilic or hydrophobic copolymer copolymerized from a so-called vinyl monomer such as a bifunctional monomer or the like can be used.

Proteins such as gelatin, derivative gelatin, colloidal albumin and casein: cellulose compounds such as carboxymethylcellulose, hydroxyethylcellulose, diacetylcellulose and triacetylcellulose; sugar derivatives such as agar, sodium alginate and starch derivatives; synthetic hydrophilic Sex colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof, and partial hydrolysates, polyvinyl acetate, polyacrylonitrile, and vinyl polymers such as polyacrylic acid esters; Natural products such as copolymers, rosin and shellac and derivatives thereof, and many other synthetic resins are used. Also, styrene-butadiene copolymer, polyacrylic acid, polyacrylate and derivatives thereof, polyvinyl acetate, vinyl acetate-acrylate copolymer, polyolefin,
Emulsions such as olefin-vinyl acetate copolymers can also be used. In addition, organic semiconductors such as carbonate-based, polyester-based, urethane-based, epoxy-based resins, polyvinyl chloride, polyvinylidene chloride, and polypyrrole can also be used. These binders can be used as a mixture of two or more kinds.

The acrylic latex used in the present invention can be produced by an emulsion polymerization method. For example, using water as a dispersion medium, 10 to 50% by mass of a monomer with respect to water and 0.05 to 5% by mass of a polymerization initiator with respect to the monomer,
0.1 to 20% by mass of a dispersant, about 30 to 100%
C., preferably 60 to 90.degree. C. for 3 to 8 hours under stirring for polymerization. Conditions such as the amount of the monomer, the amount of the polymerization initiator, the reaction temperature, and the reaction time can be widely changed.

Examples of the polymerization initiator include water-soluble peroxides (eg, potassium persulfate, ammonium persulfate, etc.) and water-soluble azo compounds (eg, 2,2′-azobis (2-aminodipropane) hydrochloride, etc.) Or these F
A redox polymerization initiator in which a reducing agent such as e ²⁺ salt or sodium bisulfite is combined can be used.

As the dispersant, a water-soluble polymer is used, and an anionic surfactant, a nonionic surfactant,
Either a cationic surfactant or an amphoteric surfactant can be used.

The acrylic latex of the present invention can be produced by using an acrylic monomer alone or by using another monomer (hereinafter, referred to as a comonomer) copolymerizable with the acrylic monomer and the acrylic monomer. .

As the acrylic monomer, for example,
Acrylic acid; methacrylic acid; acrylic acid esters such as alkyl acrylates (eg, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, t-butyl acrylate, 2
-Ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, phenyl ethyl acrylate, etc.), hydroxy-containing alkyl acrylates (for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc.); methacrylic acid esters, for example, alkyl methacrylate (for example, , Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-
Ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenylethyl methacrylate, etc., hydroxy-containing alkyl methacrylates (eg, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc.); acrylamide; substituted acrylamides (eg, N-methylacrylamide) N-methylolacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide, etc.); methacrylamide; substituted methacrylamide (for example, N-methylmethacrylamide, N-methylolmethacrylamide,
N, N-dimethylol methacrylamide, N-methoxymethyl methacrylamide, etc.); amino-substituted alkyl acrylate (eg, N, N-diethylaminoethyl acrylate); amino-substituted alkyl methacrylate (eg, N, N-diethylamino methacrylate) ;
Epoxy group-containing acrylates (eg, glycidyl acrylate); epoxy group-containing methacrylates (eg,
Glycidyl methacrylate); salts of acrylic acid (eg, sodium, potassium, ammonium salts); salts of methacrylic acid (eg, sodium, potassium,
Ammonium salts). One or more of the above-mentioned monomers can be used in combination.

Examples of the comonomer include styrene and derivatives thereof; unsaturated dicarboxylic acids (eg, itaconic acid, maleic acid, fumaric acid); esters of unsaturated dicarboxylic acids (eg, methyl itaconate, dimethyl itaconate, maleic acid) Methyl, dimethyl maleate, methyl fumarate, dimethyl fumarate); salts of unsaturated dicarboxylic acids (eg, sodium salt, potassium salt, ammonium salt); monomers containing sulfonic acid groups or salts thereof (eg, styrene sulfonic acid) , Vinylsulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt)); acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate; allyl isocyanate; vinyl methyl ether; vinyl ethyl ether; No. One or more of the above-mentioned monomers can be used in combination.

In the present invention, as the hydrophobic binder, vinyl esters, vinyl ketones, styrenes,
Hydrophobic copolymers copolymerized from so-called vinyl monomers such as diolefins and vinyl chlorides can be mentioned.

The filler used in the undercoat layer of the present invention is not particularly limited as long as it increases the elastic modulus of the binder. The filler used in the undercoat layer of the present invention may be an inorganic compound or an organic compound.

As fillers, carbon black, graphite, TiO ₂ , BaSO ₄ , ZnS, MgC
O ₃ , CaCO ₃ , ZnO, CaO, WS ₂ , MoS ₂ , M
gO, SnO ₂ , Al ₂ O ₃ , α-Fe ₂ O ₃ , α-FeO
OH, SiC, CeO ₂ , BN, SiN, MoC, B
Inorganic fillers such as C, WC, titanium carbide, corundum, artificial diamond, garnet, garnet, quartzite, triboli, diatomaceous earth, dolomite, polyethylene resin particles, fluororesin particles, guanamine resin particles, acrylic resin particles, silicon resin particles And organic fillers such as melamine resin particles.

The conductive metal oxide used in the undercoat layer of the present invention only needs to have conductivity, such as an oxygen-deficient oxide, a metal-excess oxide, a metal-deficient oxide, and an oxygen-excess oxide. Metal oxide fine particles that easily form nonstoichiometric compounds can be used. Among them, the most preferable compounds for the present invention are metal oxide fine particles which can be produced in various manners by using various methods. As the metal oxide fine particles, crystalline metal oxide particles are generally used, for example, ZnO, TiO ₂ ,
SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, B ₂
O, MoO ₃ and their composite oxides can be mentioned. Among them, ZnO, TiO ₂ , and S
nO ₂ is preferable, and as the composite oxide, Al, In, etc. for ZnO, Nb, Ta, etc. for TiO ₂ ,
Preferably, SnO ₂ contains 0.01 to 30 mol% of different elements such as Sb, Nb, and halogen elements, and particularly preferably 0.1 to 10 mol%. The volume resistivity of these conductive fine particles is preferably 10 ⁷ Ω · cm or less, particularly preferably 10 ⁵ Ω · cm or less. It is preferable to use a compound having oxygen vacancies in the crystal and a small amount of a different kind of atom serving as a so-called donor for the metal oxide because conductivity is improved. Details of the method for producing such conductive fine particles are described in, for example, JP-A-56-143430.

As the epoxy group-containing crosslinking agent used in the undercoat layer of the present invention, those containing a hydroxy group or an ether bond are preferred. In particular, an epoxy equivalent of 100
~ 300 are preferred.

Specific examples of the epoxy compound of the present invention will be given.

[0037]

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[0038]

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The oxazoline group-containing crosslinking agent used in the present invention is not particularly limited as long as it has an oxazoline group as a functional group. What consists of a containing copolymer is preferable. As such an oxazoline group-containing crosslinking agent, JP-A No. 2-6 / 1990
Nos. 0941, 2-99537 and 2-115238
No., copolymers described in JP-B-63-48884 and the like,
Alternatively, a derivative thereof can be used.

Specifically, the following general formula (1)

[0041]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl groups, and R ₅ is a non-functional group having an addition-polymerizable unsaturated bond. And a copolymer obtained by copolymerizing an addition-polymerizable oxazoline represented by the formula (1) with at least one other monomer.

Examples of the addition-polymerizable oxazoline include 2-vinyl-2-oxazoline and 2-vinyl-4-methyl-2.
-Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-
Isopropenyl-4-methyl-2-oxazoline, 2-
Isopropenyl-5-ethyl-2-oxazoline and the like can be used, and one or a mixture of two or more thereof can also be used. Among them, 2-isopropenyl-2-oxazoline is easily available industrially and is preferred.

In the present invention, the elastic modulus of the undercoat layer can be determined as follows. First, a coating solution for a layer whose elastic modulus is to be obtained is poured into a petri dish subjected to a mold release treatment, and slowly dried so as not to cause cracks. At this time, the dry film thickness is desirably 0.1 μm to 1 mm. Subsequently, after heat treatment is performed at a predetermined temperature, the film is separated as a single film. The obtained single film is subjected to a tensile test by a method shown in ASTM D638 or the like, and the elastic modulus is obtained from the initial slope of the stress-strain curve.

In the present invention, the term “compatible” refers to a state in which different polymers are uniformly mixed at the molecular level.
Specifically, a heterogeneous polymer is dissolved in a common solvent to prepare a homogeneous solution. If the sample obtained by casting this solution is transparent and uniform, it is determined that different polymers are compatible.

If there is no common solvent, different kinds of polymers are pulverized and mixed, and then heated and dissolved at a temperature higher than the melting point. When the sample is transparent and uniform when the temperature is returned to room temperature again, it is determined that different polymers are compatible.

The undercoat layer of the present invention can be formed by coating and drying using a generally well-known coating method. As a coating method that can be used,
For example, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or US Pat. No. 2,68
No. 1,294, an extrusion coating method using a hopper. Also, if necessary, U.S. Pat. Nos. 2,761,791 and 3,508,947.
Nos. 2,941,898 and 3,526,528
No., Yuji Harazaki, “Coating Engineering”, p. 253 (197)
3rd year published by Asakura Shoten Co., Ltd.) can be used.

Prior to the application of the coating solution of the present invention, the polyester support may be subjected to a pretreatment.

Since the polyester support has a regular structure in which the surface does not easily adhere, it is particularly preferable to perform a pretreatment to form the primer layer of the present invention.

The pretreatment includes a so-called etching solvent (eg, phenol, cresol, resorcin, chloral hydrate, chlorophenol, etc.) treatment for bonding the primer layer of the present invention by an anchoring effect, a mechanical treatment, a corona discharge treatment, a flame. There are surface activation treatments such as treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone treatment. When the primer layer of the present invention is provided on a polyester support, it can be provided during the formation of the polyester support, before stretching, or after stretching.

The coating amount of the coating solution of the present invention is 0.01 to 10 ml, particularly 0.1 to 3 ml, per m ^{2 in} solid volume.
It is preferred that

Drying conditions are generally at 120 to 200 ° C. for 1 hour.
It is about 0 seconds to 10 minutes. A surfactant, a swelling agent, a matting agent, a dye for crossover, an antihalation dye, a pigment, an antifoggant, a preservative, and the like may be added to the coating solution of the present invention as needed. As the swelling agent, phenol, resorcin, cresol, chlorophenol and the like are used, and the amount added is 1 to 1 liter of the coating solution of the present invention.
10 g is sufficient. As a matting agent, particle size 0.1-10μ
m, silica, polystyrene spheres, methyl methacrylate spheres and the like are preferable.

The silver halide grains in the present invention function as a light sensor. In the present invention, in order to suppress white turbidity after image formation and to obtain good image quality, it is preferable that the average particle size is small, and the average particle size is 0.1 μm or less, more preferably 0.01 μm or less.
m to 0.1 μm, particularly preferably 0.02 μm to 0.08 μm. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less. More preferably 30%
Or less, particularly preferably 0.1% or more and 20% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 In the present invention, the silver halide particles have an average particle size of 0.1.
μm or less and more preferably monodisperse particles,
By setting it in this range, the granularity of the image is also improved.

The shape of the silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is preferably high, and this proportion is 50% or more, and more preferably 7%.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is determined by the T.M. Tani, J .; Imaging Sci. , 29,
165 (1985).

Another preferred form of silver halide is tabular grains. The term “tabular grain” as used herein means a vertical thickness h μm where the square root of the projected area is a particle diameter r μm.
Means that the aspect ratio = r / h is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or less. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm.
These are disclosed in U.S. Patent Nos. 5,264,337 and 5,31.
No. 4,798, 5,320,958, and the like, the desired tabular grains can be easily obtained. When these tabular grains are used in the present invention, the sharpness of an image is further improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (Th
e Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used.
Any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source. Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide, or may be prepared by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, the silver halide is preferably contained in an amount of 0.75 to 30% by mass based on the organic silver salt.

The silver halide used in the present invention preferably contains ions or complex ions of metals belonging to Groups 6 to 10 of the periodic table. The above metals include W, Fe, Co, Ni, Cu, Ru, Rh, P
d, Re, Os, Ir, Pt, and Au are preferred.

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 represented by the following general formula.

In the formula [ML ₆ ] ^m , M is a transition metal selected from the elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0,-, 2-, 3- or Represents 4-. Specific examples of the ligand represented by L include:
Halides (fluoride, chloride, bromide and iodide),
Examples include cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide, and aquo ligands, nitrosyl, thionitrosyl, and the like, and preferably aquo, nitrosyl, and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os).

Specific examples of the transition metal coordination complex are shown below. 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^4- 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^{2 -} 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl4 (TeCN)] ^2- 23: [Ru (NS) C _5] ^2- 24: [Re (NS) Cl4 (SeCN)] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^2- 27: [Ir ( NS) Cl ₅ ] ^2- These ions or complex ions of these metals may be used alone or in combination of two or more of the same and different metals. The content of these 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 It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation.
In the addition, it may be added in several divided portions, may be uniformly contained in the silver halide grains, or may be added to the silver halide grains as described in JP-A-63-29603 and JP-A-2-3062.
No. 36, No. 3-167545, No. 4-76534,
As described in JP-A-6-110146, JP-A-5-273683, and the like, the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles. These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are mixed at the same time. To prepare silver halide grains by a method of simultaneous mixing of three liquids, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or a method of preparing silver halide. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance is sometimes added and dissolved. In particular, a method of adding an aqueous solution of a powder 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. When adding 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 at the end of physical ripening, or at the time of chemical ripening.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted. .

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448 and 3,773,512.
No. 3,593,863 and Research
Disclosure Nos. 17029 and 29996, and include: Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (for example, Np-
Methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) , Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenesulfhydroxamic acid); sulfonamidoanilines (e.g., 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Amidooxins; Azines (for example, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids; Azines and sulfone Combinations of amidophenols; α-cyanophenylacetic acid derivatives; bis-β-naphthol and 1,3-
5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (e.g., 2,6-dimethoxy-3,
5-dicarbethoxy-1,4-dihydropyridine);
Bisphenols (for example, bis (2-hydroxy-3
-T-butyl-5-methylphenyl) methane, bis (6
-Hydroxy-m-tri) mesitol
l), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,5-ethylidene-bis (2-t-
Butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols.

The amount of the reducing agent used is preferably 1 × 10 ^-2 to 10 mol, particularly 1 × 10 ^{-2 to} 1.5 mol per mol of silver.

In the present invention, the reducing agent may be directly contained in the binder, but the reducing agent may be contained in the binder in the form of water-dispersible composite fine particles with the resin.

The resins used in this case are water-insoluble copoly (styrene-acrylonitrile), copoly (styrene-styrene).
Butadiene), poly (vinyl acetal) s (for example,
Poly (vinyl formal) and poly (vinyl butyral)), poly (ester) s, poly (urethane) s, phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate) ) And cellulose esters. The method for producing the water-dispersible composite fine particles is not particularly limited as long as the reducing agent is present in the resin.For example, the reducing agent is dissolved in a solution in which these resins are dissolved, and this is dissolved in a surfactant or dispersion. It can be manufactured by dispersing in water containing the agent. Examples of the surfactant include sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium dodecylnaphthalenesulfonate, sodium dodecylbenzenesulfonate, sodium dodecylphosphate, cetyl Trimethyl ammonium chloride, dodecyl trimethylene ammonium chloride, N-2-
Examples include ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, and polyoxyethylene sorbitan laurate ester. Examples of the dispersion stabilizer include hydrophilic colloids such as gelatin, and polymer dispersants obtained by copolymerizing a monomer having a hydrophilic group. Examples of the monomer having a hydrophilic group include methacrylic acid, acrylic acid, and vinyl. Examples include pyrrolidone, acrylamide, N, N-dimethylacrylamide, maleic acid, itaconic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, acrylic acid ester having an ethylene oxide group, and methacrylic acid ester.

Examples of the binder used in the photothermographic material of the present invention include hydrophilic protective colloids and aqueous dispersions of resins. Gelatin is used as a binder for the hydrophilic colloid layer, but other hydrophilic colloids may be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate, sodium alginate, cellulose sulfate, dextrin, dextran, dextran Sugar derivatives such as sulfates, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., and various kinds such as copolymers Can be used.
As gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and a hydrolyzate of gelatin and an enzyme-decomposed product of gelatin can also be used. Examples of the aqueous dispersion of the resin include acrylic resins, polyester resins, rubbers, polyvinyl acetates, modified polyvinyl alcohol, cellulose esters, polyurethanes, polyvinyl chlorides, polyvinylidene chlorides, and the like. . Dispersions of these resins may be those obtained by dispersing the resin in water, or those obtained by polymerizing monomers in water,
Either can be used.

These binders may be used alone or in combination of two or more kinds, but it is preferable that gelatin accounts for 5% by mass or more of the whole binder.

In the present invention, in order to increase the speed of thermal development, the amount of the binder in the photosensitive layer is 1.0 to 15 g / m ^2.
It is preferred that More preferably, 1.7 to 8 g
/ M ² .

In the present invention, the photosensitive material is 80 to 14
It is characterized in that an image is formed by heat development at 0 ° C., and no fixing is performed. Therefore, the silver halide and the organic silver salt remaining in the unexposed area remain in the photosensitive material without being removed.

In the present invention, after the heat development processing,
The optical transmission density of the light-sensitive material containing the support at 400 nm is preferably 0.2 or less. A more preferable value of the optical transmission density is 0.02 or more and 0.2 or less.
If it is less than 0.02, the sensitivity may be too low to use.

In the present invention, a matting agent is preferably contained on the side of the photosensitive layer, and in order to prevent damage to the image after thermal development, it is preferable to provide a matting agent on the surface of the photosensitive material. It is preferred that the matting agent is contained in a mass ratio of 0.5 to 30% with respect to all binders on the emulsion layer side.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, inorganic substances include silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 and the like. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic matter,
Starch described in U.S. Pat. No. 2,322,037, Belgian Patent 625,451 and British Patent 981,19
No. 8 and the like, and starch derivatives described in JP-B-44-3643.
No. 33, Swiss Patent No. 33
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,16.
An organic matting agent such as polycarbonate described in No. 9 or the like can be used.

The shape of the matting agent may be either regular or irregular, but is 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. In the present invention, the particle diameter of the matting agent indicates 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 matting agent has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the variation coefficient of the particle size distribution is a value represented by the following equation. (Standard deviation of particle size) / (average value of particle size) × 100 The matting agent according to the present invention can be contained in any constituent layer, but is preferably photosensitive in order to achieve the object of the present invention. It is a constituent layer other than the layer, more preferably the outermost layer as viewed from the support.

The method of adding the matting agent according to the present invention may be a method of dispersing in a coating solution in advance and applying the solution.
A method of spraying a matting agent after the application liquid is applied and before the drying is completed may be used. When a plurality of types of matting agents are added, both methods may be used in combination.

The heat-developable photographic light-sensitive material of the present invention forms a photographic image by heat-development processing, and includes a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, It is preferable that the photothermographic material is a heat-developable photographic material containing a color tone agent for suppressing the color tone of silver in a state of being dispersed in a usual (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but after exposure to high temperatures (for example,
(80 ° C. to 140 ° C.). Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer on the same side as the photosensitive layer and / or an antihalation dye layer, a so-called backing layer, may be formed on the opposite side. A dye or a pigment may be included in the active layer. As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range, and examples thereof include JP-A-59-6481 and JP-A-59-18.
2436, U.S. Pat. No. 4,271,263, U.S. Pat. No. 4,594,312, EP 533008,
European Patent Publication No. 652473, JP-A-2-216140
JP-A-4-348339, JP-A-7-19143
No. 2, JP-A-7-301890 and the like are preferably used.

These non-photosensitive layers preferably contain the binder and the matting agent described above, and may further contain a sliding agent such as a polysiloxane compound, wax or liquid paraffin.

The light-sensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

It is preferred to add a toning agent to the photothermographic material of the present invention for the purpose of improving the silver tone after development. Examples of suitable toning agents are Research Disc
No. 17029, which includes the following:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); phthalazone, a phthalazone derivative or a metal salt of these derivatives (for example, 4- (1-
Naphthyl) phthalazone, 6-chlorophthalazone, 5,7
-Dimethyloxyphthalazone and 2,3-dihydro-
1,4-phthalazinedione); a combination of phthalazone and a sulfinic acid derivative (eg, 6-chlorophthalazone + sodium benzenesulfinate or 8-methylphthalazone + sodium p-trisulfonate); a combination of phthalazine + phthalic acid; phthalazine (of phthalazine) Adducts), maleic anhydride, and phthalic acid, 2,
A combination with at least one compound selected from 3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (eg,
2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,6-dimercapto-1,
4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained in order to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to.

When a mercapto compound is used in the present invention, it may be of any structure,
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1-4 carbon atoms) and alkoxy (eg, For example, it may have one selected from a substituent group consisting of one or more carbon atoms, preferably one having 1 to 4 carbon atoms. Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole,
-Mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole,
2-mercaptoquinoline, 8-mercaptopurine, 2,
3,5,6-tetrachloro-4-pyridinethiol,
-Hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole and the like,
The present invention is not limited to these.

The photothermographic material of the present invention may contain an antifoggant. What is known as the most effective antifoggant is mercury ion. The use of a mercury compound as an antifoggant in a light-sensitive material is disclosed in, for example, US Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly.
Non-mercury antifoggants include, for example, US Pat.
Preferred are antifoggants as disclosed in US Pat. Nos. 6,075 and 4,452,885 and JP-A-59-57234.

Particularly preferred non-mercury antifoggants are disclosed in US Pat. Nos. 3,874,946 and 4,756,99.
No.9, -C (X ₁ )
(X ₂ ) A heterocyclic compound having one or more substituents represented by (X ₃ ) (where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen). Examples of suitable antifoggants include JP-A-9-288328, paragraph [0030].
To [0036] are preferably used. Examples of another preferred antifoggant include paragraphs [0062] to JP-A-9-90550.
[0063] The compound described in [0063]. Still other suitable antifoggants are disclosed in US Pat. No. 5,028,5.
No. 23 and British Patent Application Nos. 92221383.4, 9300147.7 and 9311790.1.

The heat-developable photographic light-sensitive material of the present invention includes, for example, JP-A-63-159814 and JP-A-60-140335.
No. 63-231437, No. 63-296551
No. 63-304242, No. 63-15245,
U.S. Pat. Nos. 4,639,414 and 4,740,4
No. 55, No. 4,741,966, No. 4,751,
No. 175 and No. 4,835,096. Useful sensitizing dyes for use in the present invention include, for example, Research DisclosureIt
em17643 IV-A (p.2 December 1978)
3), Item 1831X (August 1978, p. 4
37) or in the literature cited. 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, compounds described in JP-A-9-34078, JP-A-9-54409 and JP-A-9-80679 are preferably used.

The various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid. These additives and the other additives mentioned above are available from Research Disclosure Item.
m17029 (p. 9-15, June 1978) can be preferably used.

In the heat-developable material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method, or the like can be used.
See Research Disclosure, 176
Vol. 27-28 “Coating processed”
ures "section.

[0093]

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

Example 1 (Sample 1) [Preparation of Subbed Support] 10 W / m ² · mi on both sides of a biaxially stretched polyethylene terephthalate film
n, a corona discharge treatment was performed under the condition of n, and the following <coating solution for backcoat-side undercoating lower layer> was applied on one surface to a dry film thickness of 0.06.
After coating to a thickness of μm, the coating was dried at 140 ° C. Then, the following “coating solution for the backcoat-side undercoating upper layer” was coated to a dry film thickness of 0.4 μm, and then dried at 140 ° C. On the other side, the following <Emulsion side undercoating underlayer coating solution> was applied so as to have a dry film thickness of 0.4 μm.
After drying at 0 ° C., and then applying the following “coating solution for undercoating upper layer on emulsion side” to a dry film thickness of 0.2 μm,
Dried at 0 ° C. These are heat-treated at 125 ° C. for 2 minutes,
A subbed support was prepared.

<< Coating Solution for Undercoating Lower Layer on Backcoat Side >> a-1 (solid content 30%) 12.0 g a-2 (solid content 30%) 3.0 g SnO ₂ sol (solid content 10%) 86 g (special (Synthesized by the method described in Kaihei 10-059720) Surfactant (A) 0.4 g or more was added with distilled water to make 1000 ml, thereby obtaining a coating solution.

<< Coating Solution for Undercoating Upper Layer on Backcoat Side >> a-2 (solid content: 30%) 130 g Surfactant (A) 0.4 g Silica fine particles (average particle size 2 μm) Distilled water was added to 0.3 g or more. To 1000 ml to prepare a coating solution.

<< Coating Solution for Emulsion Side Subbing Underlayer >> a-1 (solid content 30%) 5 g a-5 (solid content 30%) 95 g surfactant (A) 0.3 g Distilled water was added to 1000 g or more, and 1000 ml To obtain a coating solution.

<< Coating Liquid for Emulsion Side Subbing Upper Layer >> a-2 (solid content 30%) 70 g Surfactant (A) 0.3 g Silica fine particles (average particle size 2 μm) Distilled water was added to 0.3 g or more. 1000 ml was used as a coating solution.

[0099]

Embedded image

[0100]

[Table 1]

[Coating of Emulsion Layer and Backcoat Layer] (Preparation of Silver Halide Emulsion A) In 900 ml of water, 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved, and the temperature was adjusted to 35 ° C. and the pH was adjusted to 3.0. After adjusting to, silver nitrate 74
g of an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (98/2) and [Ir (N
O) Cl ₅ ] salt was added in an amount of 1 × 10 ⁻⁶ mol per mol of silver, and the rhodium chloride salt was added in an amount of 1 × 10 ⁻⁴ mol per mol of silver.
While maintaining g7.7, it was added by a controlled double jet method. Thereafter, 4-hydroxy-6-methyl-1,
Add 3,3a, 7-tetrazaindene and add NaOH to p.
By adjusting H to 5, cubic silver iodobromide grains having an average grain size of 0.06 μm, a monodispersity of 10%, a variation coefficient of projected diameter area of 8%, and a [100] face ratio of 87% were obtained. After coagulating and sedimenting this emulsion using a gelatin coagulant and desalting, 0.1 g of phenoxyethanol was added, pH 5.9, pAg7.
Adjusted to 5 to obtain a silver halide emulsion A. Further, chemical sensitization was performed with chloroauric acid and inorganic sulfur.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at a high speed, 98 ml of a 1.5 M aqueous sodium hydroxide solution
Was added. Next, 0.93 ml of concentrated nitric acid was added.
C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion of Silver Behenate and Silver Halide A) 15.1 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. 147m of 1M silver nitrate solution
was added over 7 minutes, and the mixture was further stirred for 20 minutes, and the water-soluble salts were removed by ultrafiltration. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion was formed, the water was removed, washed with water six times and water was removed, and dried.

(Preparation of photosensitive emulsion) Polyvinyl butyral (average molecular weight: 300
544 g of a methyl ethyl ketone solution (0%) (17% by mass)
And 107 g of toluene were gradually added and mixed.
Dispersed at 000 rps. The following layers were sequentially formed on the support to prepare a sample. In addition, drying is 60
C. for 15 minutes.

Back side coating: A solution having the following composition was applied. Cellulose acetate (10% methyl ethyl ketone solution) 15 ml / m ² dye-B 7 mg / m ² dye-C 7 mg / m ² Matting agent: monodispersity 15% average particle size 10 μm monodisperse silica 30 mg / m ² C ₉ H ₁₇ − C ₆ H ₄ —SO ₃ Na 10 mg / m ²

[0106]

Embedded image

Photosensitive layer surface side coating Photosensitive layer 1: A solution having the following composition was coated and the silver amount was 2.1 g / m ^2.
It was applied so that it became.

Preform emulsion 240 g Sensitizing dye-1 (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Fog Inhibitor-2 (10% methanol solution) 1.2 ml 2- (4-chlorobenzoyl) benzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline ( 5% methanol solution) 17 ml Developer-1 (20% methanol solution) 29.5 ml

[0109]

Embedded image

Surface protective layer: A solution having the following composition was applied on the photosensitive layer. Acetone 35 ml / m ² Methyl ethyl ketone 17 ml / m ² Cellulose acetate 2.3 g / m ² Methanol 7 ml / m ² Phthalazine 250 mg / m ² 4-Methylphthalic acid 180 mg / m ² Tetrachlorophthalic acid 150 mg / m ² Tetrachlorophthalic anhydride 170 mg / m ² matting agent: monodispersity 10% average particle size 4 μm monodisperse silica 70 mg / m ² C ₉ H ₁₇ -C ₆ H ₄ —SO ₃ Na 10 mg / m ² (samples 2, 3, and 4) sample 1 The coating was prepared in the same manner as in Sample 1 except that the binder contained in << Coating solution for backcoat-side undercoating lower layer >> and << Coating solution for backcoat-side undercoating upper layer >> and the film thickness were changed according to Tables 2 and 3.

(Sample 5) Sample 1 was prepared in the same manner as in Sample 1 except that the “coating solution for the undercoating lower layer on the back coat side” was changed to the following coating solution.
It was prepared in the same manner as

A-1 (solid content 30%) 20 g a-2 (solid content 30%) 5 g SiO ₂ sol (Nissan Chemical Snowtex 20, solid content 20%) 65 g Surfactant (A) 0.3 g or more Was added to distilled water to make 1000 ml to obtain a coating solution.

(Sample 6) A sample was prepared in the same manner as in Sample 1 except that the SnO ₂ sol was removed from the << Coating solution for the undercoating lower layer on Sample 1 >>.

(Sample 7) Sample 1 was prepared in the same manner as in Sample 1 except that the “coating solution for the undercoating upper layer on the back coat side” was changed to the following coating solution.
It was prepared in the same manner as

A-2 (solid content: 30%) 15.0 g SnO ₂ sol (solid content: 10%) 86 g (synthesized by the method described in JP-A-10-059720) Surfactant (A) 0.4 g Distilled to 0.4 g or more Water was added to make up to 1000 ml to make a coating solution.

Tables 2 and 3 show the results of evaluation on the back coat side of the above samples. Evaluation method (exposure and development processing)
Exposure was performed by an imager having a semiconductor laser. Then, using an automatic developing machine having a heat drum,
C. for 15 seconds. At that time, exposure and development are 2
The test was performed in a room conditioned at 3 ° C. and 50% RH.

(With backcoat layer film) A cellophane adhesive tape was pressure-bonded to the backcoat layer side of the sample before and after the heat development treatment, and the sample was rapidly peeled off to obtain the peeled area of the backcoat layer. The evaluation was performed according to evaluation criteria.

Evaluation Criteria 1. Adhesive strength is very weak, and the back coat layer is completely peeled off. 2. The peeled area is 50% or more and less than 100%. 3. The peeled area is 20% or more and less than 50%. 4. The adhesive strength is strong, and the peeled area is 5% or more and less than 20%. Adhesive strength is very strong, and the peeled area is less than 5%. When the rating is 4 or more, it can be considered that the film is sufficiently strong for practical use.

(Surface Resistivity of Subbed Base) Measured at 23 ° C. and 20% RH using Teraohmmeter Model VE-30 manufactured by Kawaguchi Electric Co., Ltd.

[0120]

[Table 2]

[0121]

[Table 3]

Tables 2 and 3 show that the sample of the present invention is superior to the comparison. Example 2 (Samples 10 and 11) A sample was prepared in the same manner as in Sample 1 except that the binder contained in << Coating Solution for Emulsion Side Subbing Upper Layer >> of Sample 1 was changed according to Table 4.

(Sample 12) A sample was prepared in the same manner as in Sample 1, except that the "coating solution for the undercoating layer on the emulsion side" of Sample 1 was changed to the following coating solution.

Gelatin 20 g Surfactant (A) 0.3 g Silica fine particles (average particle diameter 2 μm) 0.3 g or more was added to distilled water to make 1000 ml to prepare a coating solution.

(Sample 13) A sample was prepared in the same manner as in Sample 1, except that the "coating solution for the undercoating layer on the emulsion side" of Sample 1 was changed to the following coating solution.

Gelatin 20 g Butyral resin (water-soluble polyvinyl butyral BW-3 manufactured by Denki Kagaku Kogyo, solid content 13%) 7.7 g Surfactant (A) 0.3 g Silica fine particles (average particle size 2 μm) 0.3 g or more Distilled water was added to make up to 1000 ml to make a coating solution.

(Sample 14) A sample was prepared in the same manner as in Sample 1, except that "Coating solution for emulsion-side undercoating upper layer" of Sample 1 was changed to the following coating solution.

Gelatin 20 g Butyral resin (water-soluble polyvinyl butyral BW-3 manufactured by Denki Kagaku Kogyo, solid content 13%) 3.0 g (2%) Surfactant (A) 0.3 g Silica fine particles (average particle size 2 μm) 0 Distilled water was added to 0.3 g or more to make 1000 ml to prepare a coating solution.

Table 4 shows the results of the evaluation on the emulsion side of the above samples. Evaluation method (exposure and development treatment) The same treatment as in Example 1 was performed.

(Emulsion layer film attached) A cellophane adhesive tape was pressed against the silver halide emulsion layer side of the sample before and after the heat development processing, and the sample was rapidly peeled off to obtain a peeled area of the silver halide emulsion layer. The evaluation was performed according to the following evaluation criteria.

Evaluation Criteria 1. The adhesion is very weak, and the silver halide emulsion layer is completely peeled off. 2. The peeled area is 50% or more and less than 100%. 3. The peeled area is 20% or more and less than 50%. 4. The adhesive strength is strong, and the peeled area is 5% or more and less than 20%. Adhesive strength is very strong, and the peeled area is less than 5%. When the rating is 4 or more, it can be considered that the film is sufficiently strong for practical use.

(Emulsion coating property) Emulsion coating property on the undercoating surface was evaluated by the number of coating streaks generated per 1 m of coating width and 1 m of coating length. When the number of streaks is 0 to 1, there is no practical problem.

[0133]

[Table 4]

Table 4 shows that the sample of the present invention is superior to the comparison. Example 3 (Sample 20) [Preparation of Subbed Support] 8 W / m ² min on both sides of biaxially stretched polyethylene terephthalate film
Under the conditions described above, and on one surface, the following <coating solution for backcoat-side undercoating lower layer> is dried to a thickness of 0.06 μm.
m, and then dried at 140 ° C. Subsequently, the following “coating solution for backcoat-side undercoating upper layer” was applied so as to have a dry film thickness of 0.03 μm, and then dried at 140 ° C. On the other side, the following <Emulsion side undercoating underlayer coating solution> was applied so as to have a dry film thickness of 0.2 μm.
After drying at 0 ° C., and then applying the following “coating solution for an emulsion-side undercoating upper layer” to a dry film thickness of 0.03 μm,
Dried at 40 ° C. These were heat-treated at 140 ° C. for 2 minutes to produce an undercoated support.

<< Coating Solution for Undercoating Lower Layer on Backcoat Side >> a-1 (solid content 30%) 12.0 g a-2 (solid content 30%) 3.0 g SnO ₂ sol (solid content 10%) 86 g (special (Synthesized by the method described in Kaihei 10-059720) Surfactant (A) 0.4 g or more was added to distilled water to make 1000 ml to prepare a coating solution.

<< Coating Liquid for Undercoating Upper Layer on Backcoat Side >> Water-soluble polymer (A) 3.0 g Surfactant (A) 0.4 g Hardener (A) 0.3 g Silica fine particles (average particle diameter 2 μm) 0 Distilled water was added to 0.3 g or more to make 1000 ml to prepare a coating solution.

<< Emulsion Side Undercoat Coating Solution >> a-1 (solid content 30%) 30 g a-3 (solid content 30%) 70 g surfactant A 0.3 g hardener (B) 2.8 g or more Was added to distilled water to make 1000 ml to obtain a coating solution.

<< Coating Solution for Emulsion Side Subbing Upper Layer >> Water-soluble polymer (A) 3.0 g Surfactant (A) 0.4 g Hardener (A) 0.3 g Silica fine particles (average particle size 2 μm) Distilled water was added to 3 g or more to make 1000 ml to prepare a coating solution.

[0139]

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[Coating of emulsion layer and back coat layer] [Preparation of organic silver salt] 40 g of behenic acid and stearic acid 7.
3 g and 500 ml of water were stirred at a temperature of 90 ° C. for 15 minutes.
187 ml of N-NaOH are added over 15 minutes and 1N
Of nitric acid aqueous solution was added and the temperature was lowered to 50 ° C. Next, 124 ml of 1N silver nitrate aqueous solution is added over 2 minutes,
The mixture was stirred for 30 minutes as it was. Thereafter, the solid content was separated by suction filtration, and the solid content was further washed with water and dried.

[Preparation of Aqueous Dispersible Organic Silver Salt Composite Fine Particles (FG-1)] 10 g of sodium diethylhexylsulfosuccinate was dissolved in 252 g of distilled water, and 36.4 g of the above organic silver salt was added thereto while stirring. An ultrasonic element was introduced into the container and dispersed. 5.5 g of methyl methacrylate (MMA), 5.0 g of ethylene glycol dimethacrylate (EGDMA), 6.0 g of stearyl methacrylate (SMA), 0.6 g of hexadecane,
2'-azobis (2,4-dimethylvaleronitrile)
0.9 g of the mixture was added and further dispersed ultrasonically. To 50 g of the dispersion, 25 g of a 10% by mass aqueous solution of polyvinylpyrrolidone was added, followed by stirring while introducing nitrogen. The resulting dispersion was transferred to a 1-liter three-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer. 53 while stirring under air current
The polymerization reaction was performed at 15 ° C. for 15 hours to obtain aqueous dispersible organic silver salt composite fine particles (solid content: 19.9% by mass). The residual monomer amount in the obtained dispersion was less than 1%. The average particle size of the aqueous dispersible organic silver salt composite fine particles was 190 nm.

[Preparation of heat-developable silver halide photographic light-sensitive material] The support thus prepared was provided with the following image forming layer.

The image forming layer was coated so that the coating amount of the following emulsion layer coating solution was 2.1 g / m ^2, and the back layer was coated such that the gelatin of the following back layer coating solution was 2 g / m ^2. did. A protective layer was applied on the image forming layer and the back layer so that each material had the following coating amount.

<< Preparation of Silver Halide Emulsion B >> Water 700 m
7.5 g of inert gelatin (phthalated gelatin 2
2 g) and 10 mg of potassium bromide were dissolved at a temperature of 35.
After adjusting the pH and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate, an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (98/2) and [Ir (NO) C
l _5] salt per mole silver 1 × 10 ^{- 6} moles and 1 × 10 ^-4 mol per mol of silver rhodium chloride salt, PAG7.
While maintaining at 7, the addition was performed by the controlled double jet method. Thereafter, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene was added and the pH was adjusted to 5 with NaOH.
Adjusted to an average particle size of 0.06 μm and a monodispersity of 10
% Projection diameter area variation coefficient 8%, [100] face ratio 8
7% of cubic silver iodobromide grains were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5 to obtain a silver halide emulsion B. Further, chemical sensitization was performed with chloroauric acid and inorganic sulfur.

<< Preparation of Emulsion Layer Coating Solution >> A gelatin solution was prepared by dissolving gelatin as a binder in water.
/ 2 (mass ratio) was used as a solid mixture, and the mass was replaced with a water-dispersible polymer (LX-2). Here, LX-2: 5-sodium dimethyl sulfoisophthalate / dimethyl isophthalate / dimethyl adipate / dimethyl terephthalate (5/10/10/75 mass ratio) and ethylene glycol / polyethylene glycol (95/5 mass ratio) )) Copolyester latex (solid content 30% by mass) Binder 72 g Pure water 140 g Organic silver salt (FG-1) 1 mol of silver = 6173 g Silver halide emulsion B 0.1 mol of silver Reducing agent (RG-1 below) 2000 g tetrachlorophthalic acid 5 g phthalazine 9.2 g tribromomethylphenylsulfone 12 g 4-methylphthalic acid 7 g [Preparation of water-dispersible reducing agent-containing composite fine particles RG-1] To 405 g of ethyl acetate, 92 g of butyral resin and 1,1-bis (Hydroxy-3,5-dimethylphenyl) -3,
98 g of 5,5-trimethylhexane was dissolved and added to 1800 g of a 4% by mass gelatin solution to which 12 g of sodium dioctylsulfonesuccinate had been added. Composite reducing agent-containing composite fine particles were obtained.

<Application of Back Layer Coating Solution><< Preparation of Coloring Agent Dispersion >> Ethyl acetate 35 g Compound 1 2.5 g Compound 2 7.5 g Polyvinyl alcohol (10% by mass aqueous solution) 50 g First, the above compound 2 was stirred. To make a solution. The polyvinyl alcohol was added thereto and stirred with a homogenizer for 5 minutes. Thereafter, the solvent was volatilized by depressurizing the ethyl acetate, and finally diluted to 1 liter with water to prepare a color former dispersion.

<< Preparation of Back Layer Coating Solution >> Water 500 g Gelatin 30 g 2-acetoacetoxyethyl methacrylate / butyl acrylate / styrene (40/20/40, by mass ratio) Active methylene group-containing latex (Lx-1) (solid content) 20 g%) 50 g Color former dispersion (above) 50 g Compound 3 20 g Silica (spherical particles having an average particle diameter of 10 μm) 1.5 g

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<< Preparation of Coating Solution for Protective Layer and Formation of Protective Layer >> The following protective layer was prepared, coated on the emulsion layer and the back layer in the following coating amount (one side), and dried to obtain a sample. .

Gelatin 0.4 g / m ² polymethyl methacrylate (matting agent area average particle size 7.0 μm) 50 mg / m ² formaldehyde 10 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² bis - vinylsulfonyl methyl ether 18 mg / m ² active methylene group-containing latex (Lx-1) 0.1g / m 2 polyacrylamide (average molecular weight 10000) 0.05g / m ² of sodium polyacrylate 20mg / m ² polysiloxane (S1) 20 mg / m ² surfactant (A) 12 mg / m ² compound (J) 2 mg / m ² compound (S1) 7 mg / m ² compound (K) 15 mg / m ² compound ( _{^{O) 50mg / m 2 C 9}} F 19 O (CH 2 CH 2 O) 11 H 3mg / m 2 C 8 F 17 SO 2 N (C 3 H 7) (C _{2 CH 2 O) 15 H 2mg} / m 2 C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 SO 3 Na 1mg / m 2 hardener (C) 1.5 mg / m ²

[0151]

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(Sample 21) Sample 20 was prepared in the same manner as in Sample 20, except that the “coating solution for the undercoating upper layer on the back coat side” of Sample 20 was changed to the following coating solution and applied so that the dry film thickness became 0.05 μm. Produced.

Gelatin 10.0 g Surfactant (A) 0.3 g Hardener D 0.1 g Silica fine particles (average particle size 2 μm) 0.3 g Distilled water was added to the above to make 1000 ml, and the mixture was used as a coating solution.

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(Sample 22) The same as Sample 20 except that the “coating solution for the undercoating upper layer on the back coat side” of Sample 20 was changed to the following coating solution and applied so that the dry film thickness was 0.2 μm. Produced.

A-6 (solid content: 30%) 7.5 g Surfactant (A) 0.3 g Silica fine particles (average particle size: 2 μm) 0.3 g Distilled water was added to the above to make 1000 ml, thereby preparing a coating solution.

(Sample 23) A sample 20 was prepared in the same manner as in Sample 20, except that the coating liquid for undercoating upper layer on the back coat side of Sample 20 was applied so as to have a dry film thickness of 0.1 μm.

Table 5 shows the results of evaluation of the above samples on the back coat side. Evaluation method (exposure and development treatment) The same treatment as in Example 1 was performed.

(With Backcoat Film) Evaluation was performed in the same manner as in Example 1.

(Haze of Subtracted Base) Using a turbidimeter Model-t-2600DA manufactured by Tokyo Denshoku Co., Ltd.
The sample was measured and the haze was expressed in%.

[0161]

[Table 5]

Table 5 shows that the sample of the present invention is superior to the comparison. Example 4 (Sample 31) << Coating solution for subbing upper layer on emulsion side >>
Was prepared in the same manner as in Sample 20, except that was changed to the following coating solution.

Gelatin 10.0 g Surfactant (A) 0.3 g Hardener (D) 0.1 g Silica fine particles (average particle size 2 μm) 0.3 g or more was added to distilled water to make 1000 ml, and used as a coating solution. .

(Sample 32) A sample was prepared in the same manner as in Sample 20, except that "Coating solution for undercoating underlayer on emulsion side" of Sample 20 was changed to the following coating solution.

A-1 (solid content 30%) 30 g a-3 (solid content 30%) 70 g surfactant (A) 0.3 g 2-isopropenyl-2-oxazoline 3.0 g 1000 ml was used as a coating solution.

(Sample 33) A sample was prepared in the same manner as in Sample 20, except that the hardener was removed from << Coating solution for undercoating layer on emulsion side >> of Sample 20. Table 6 shows the results of the evaluation of the above samples on the emulsion side. Evaluation method (exposure and development treatment) The same treatment as in Example 1 was performed.

(With Emulsion Layer Film) Evaluation was made in the same manner as in Example 2.

(Scratch) A sapphire needle having a tip with a radius of curvature of 0.15 mm was applied at right angles to a sample which had been subjected to thermal development and conditioned for 24 hours at 23 ° C. and 55% relative humidity. While moving the sample in min, the load applied to the sapphire needle was gradually increased from 0 g to 200 g. The load when the scratch reaches the polyester support was evaluated as an index of scratch resistance, and 200 g or more was evaluated as a favorable level, and 100 g or less was evaluated as a practically unusable level.

[0169]

[Table 6]

From Table 6, it can be seen that the sample of the present invention is superior to the comparison.

[0171]

According to the present invention, a heat-developable photographic light-sensitive material having an undercoat layer having excellent adhesion even when heated can be provided.

Claims (9)

[Claims] In a photothermographic material having at least one undercoat layer on at least one surface of a polyester support, the lowermost undercoat layer has an elastic modulus of 1 × 10 ⁹ N /.
m ² or more, and the elastic modulus of the undercoating uppermost layer is 1 × 10 ⁹
A heat-developable photographic light-sensitive material, wherein the photographic light-sensitive material is less than N / m ² . 2. A photothermographic material having at least one undercoat layer on at least one surface of a polyester support, wherein the lowermost undercoat layer contains a filler. 3. A photothermographic material having at least one undercoat layer on at least one surface of a polyester support, wherein the lowermost undercoat layer contains a conductive metal oxide. Photosensitive material. 4. In a photothermographic material having at least two undercoat layers on at least one surface of a polyester support, an undercoat uppermost layer is provided adjacent to and above the undercoat uppermost layer. A photothermographic material containing at least 5% by mass or more of a binder constituting a layer. 5. A photothermographic material having at least one undercoat layer on at least one surface of a polyester support, wherein the undercoat uppermost layer is coated adjacent to the undercoat uppermost layer. A photothermographic material which swells or dissolves in a solvent of a liquid. 6. A photothermographic material having at least one undercoat layer on at least one surface of a polyester support, wherein the binder constituting the uppermost undercoat layer is:
A heat-developable photographic light-sensitive material, which is compatible with a binder constituting a layer coated adjacently on the uppermost subbing layer. 7. A photothermographic material having an undercoat layer on at least one surface of a polyester support, wherein at least one of the undercoat layers has a hydrophilic binder as a main component and a dry film thickness of 0.05 μm. A photothermographic material which is characterized by the following: 8. A photothermographic material having an undercoat layer on at least one surface of a polyester support, wherein at least one of the undercoat layers contains at least two kinds of acrylic polymer latex and an epoxy group-containing crosslinking agent. The glass transition temperature (TgL) of the acrylic polymer latex exhibiting the lowest glass transition temperature and the glass transition temperature (Tg) of the acrylic polymer latex exhibiting the highest glass transition temperature among the acrylic polymer latexes.
gH) is from 10 to 80C. 9. A photothermographic material having an undercoat layer on at least one surface of a polyester support, wherein at least one of the undercoat layers contains at least two kinds of acrylic polymer latex and an oxazoline group-containing crosslinking agent. And the difference between the glass transition temperature (TgL) of the acrylic polymer latex exhibiting the lowest glass transition temperature and the glass transition temperature (TgH) of the acrylic polymer latex exhibiting the highest glass transition temperature among the acrylic polymer latexes. Is a temperature of 10 to 80 ° C.