DE69922329T2 - Photothermographic or thermographic material - Google Patents

Abstract

An image-recording material which has at least on one surface side of a support a thermosensitive recording element containing a scaly organic acid silver salt, a reducing agent for a silver ion, and a binder, or a photosensitive recording element containing a scaly organic acid silver salt, a reducing agent for a silver ion, photosensitive silver halide, and a binder, wherein the NH4 <+> content of all the layers on the surface side of the support which contains the thermosensitive recording element is from 0.06 to 3.4 mmol as the coating amount per m<2> of the support.

Description

FIELD OF THE INVENTION

The The present invention relates to an image recording material and in particular a photothermographic or thermographic material with excellent silver tint.

BACKGROUND OF THE INVENTION:

One Photothermographic or thermographic material became long ago and is described, for example, in the US patents 3,152,904 and 3,457,075, D. Klosterboer, Thermally Processed Silver System, "Imaging Process and Materials ", compiled by Sturge, V. Walworth, A. Shepp, 8th Edition, Neblette, page 279 (1989). A photothermographic material generally has a Photosensitive layer, which is a catalytically effective amount a photocatalyst (e.g., silver halide), a reducing agent, a reducible silver salt (e.g., organic silver salt) and a Tints, the silver tint as required, dispersed in a binder matrix. A photothermographic material forms a silver image in black Color by heating to a high temperature (e.g., 80 ° C or more) after image exposure, whereby an oxidation-reduction reaction between silver halide or a reducible silver salt (the acts as an oxidizing agent) and a reducing agent is effected. The oxidation-reduction reaction becomes due to the catalytic action the silver halide latent image formed by the exposure accelerated. This will make a black silver image in the exposure area generated.

One Photothermographic material usually becomes after coating stored until processed and delivered as a mass product. The storage stability of the coated mass product during this time is not good and the storage stability improvement is desirable. It is further he wishes, that staining of the silver image not by the photothermographic temperature changed becomes.

SUMMARY OF THE INVENTION:

One inventive The aim is to improve the storage stability of a coated mass-produced product and the silver tint in a (photo) thermographic material, in particular a photothermographic Material.

• (1) Ein Bildaufzeichnungsmaterial, das mindestens auf einer Oberflächenseite eines Trägers ein wärmeempfindliches Aufzeichnungselement aufweist, das ein schuppenartiges Silbersalz einer organischen Säure, ein Reduktionsmittel für Silberionen und ein Bindemittel enthält, oder ein fotoempfindliches Aufzeichnungselement, das ein schuppenartiges Silbersalz einer organischen Säure, ein Reduktionsmittel für Silberionen, ein fotoempfindliches Silberhalogenid und ein Bindemittel enthält, worin der NH₄ ⁺-Gehalt aller Schichten auf der Oberflächenseite des Träges, der das wärmeempfindliche oder fotoempfindliche Aufzeichnungselement aufweist, 0,06-3,4 mmol als Beschichtungsmenge pro m² des Trägers beträgt.
• (2) Ein Bildaufzeichnungsmaterial, das mindestens auf einer Oberflächenseite eines Trägers ein wärmeempfindliches Aufzeichnungselement aufweist, das folgendes enthält: ein schuppenartiges Silbersalz einer organischen Säure, worin der Ausdruck "schuppenartiges Silbersalz einer organischen Säure" ein Silbersalz einer organischen Säure mit einer Form, die angenähert ein rechtwinkliges Parallelopiped darstellt, bedeutet, und wenn die Seiten des rechtwinkligen Parallelopipeds, ausgehend von der kürzesten, als a, b und c angenommen werden (c kann gleich b sein), wird x aus den kürzeren numerischen Werten a und b wie folgt berechnet: x = b/ax wird für etwa 200 Partikel durch die obige Gleichung erhalten, und wenn der Mittelwert als x (Durchschnitt) genommen wird, werden solche als schuppenartige Partikel betrachtet, die die Beziehung x (Durchschnitt) > 1,5 erfüllen, ein Reduktionsmittel für ein Silberion und ein Bindemittel, oder ein fotoempfindliches Aufzeichnungselement, das folgendes enthält: ein schuppenartiges Silbersalz einer organischen Säure, ein Reduktionsmittel für ein Silberion, fotoempfindliches Silberhalogenid und ein Bindemittel, worin der Alkalimetallionengehalt aller Schichten auf der Oberflächenseite des Trägers, der das wärmeempfindliche oder fotoempfindliche Aufzeichnungselement aufweist, 0,05-3,6 mmol als Beschichtungsmenge pro m² des Trägers ist.
• (3) Das Material wie oben unter (1) und (2) beschrieben, worin das Verhältnis der Gehalte an Alkalimetallion und NH₄ ⁺ als Molverhältnis von (NH₄ ⁺)/(Alkalimetallion) 0,01-30 beträgt.
• (4) Das Material wie oben unter (1) oder (3) beschrieben, worin der NH₄ ⁺-Gehalt 0,55-2,8 mmol als Beschichtungsmenge pro m² des Trägers ist.
• (5) Das Material wie oben unter (2) oder (3) beschrieben, worin der Alkalimetallionengehalt 0,59-3,0 mmol als Beschichtungsmenge pro m² des Trägers ist.
• (6) Das Material wie oben unter (2), (3) und (5) beschrieben, worin das Alkalimetallion Li⁺, Na⁺ oder K⁺ ist.
• (7) Das Material wie oben unter (3) beschrieben, worin das Verhältnis von (NH₄ ⁺)/(Alkalimetallion) 0,1-20 ist.
• (8) Das Material wie oben unter (3) beschrieben, worin das Verhältnis von (NH₄ ⁺)/(Alkalimetallion) 0,5-5 ist.
• (9) Das Material wie oben unter irgendeinem der Punkte (1) bis (8) beschrieben, worin die Schicht, die ein schuppenartiges Silbersalz einer organischen Säure enthält, ferner eine Phthalsäureverbindung enthält, die durch Formel (I) dargestellt ist:
  
  worin R₁, R₂, R₃ und R₄ jeweils ein Wasserstoffatom oder einen einwertigen Substituenten darstellen; L₁ und L₂ jeweils eine Verknüpfungsgruppe darstellen; n1 und n2 jeweils 0 oder 1 sind; M ein Wasserstoffatom oder ein Gegenion darstellt; und k eine Valenz von M darstellt, und wenn M ein Wasserstoffatom darstellt, ist k 1, vorausgesetzt dass, wenn M ein Wasserstoffatom darstellt und n1 und n2 jeweils 0 sind, R₁, R₂, R₃ und R₄ nicht alle ein Wasserstoffatom sind.
• (10) Das Material wie oben unter (9) beschrieben, worin M in Formel (I) ein Ammoniumion, ein Alkalimetallion, ein Erdalkalimetallion, ein Aluminiumion, ein Zinkion, ein ionisches Polymer, eine organische Verbindung mit entgegengesetzter Ladung oder ein Metallkomplexion darstellt.
• (11) Das Material wie oben unter irgendeinem der Punkte (1) bis (10) beschrieben, worin der Silberbehenatgehalt des Silbersalzes der organischen Säure 92 mol-% oder mehr ist.
• (12) Das Material wie oben unter irgendeinem der Punkte (1) bis (11) beschrieben, worin die Schicht, die das schuppenartige Silbersalz einer organischen Säure enthält, gebildet wird durch Aufschichten einer Beschichtungslösung, worin 30 Gew.% oder mehr des Lösungsmittels Wasser ist, und anschliessendes Trocknen, und das Hauptbindemittel dieser Schicht ein Polymer mit einem Gleichgewichtsfeuchtigkeitsgehalt bei 25°C, 60 % RH von 2 Gew.% oder weniger ist.
• (13) Das Material wie oben unter irgendeinem der Punkte (1) bis (12) beschrieben, worin das Material ein fotoempfindliches Aufzeichnungselement enthält.
• (14) Das Material wie oben unter (13) beschrieben, worin das Material zwei oder mehr Aufbauschichten aufweist, die das fotoempfindliche Aufzeichnungselement auf derselben Oberflächenseite des Trägers enthalten, auf der das fotoempfindliche Aufzeichnungselement bereitgestellt wird, und diese zwei oder mehr Aufbauschichten gleichzeitig aufgeschichtet werden.

The above object of the present invention has been achieved by the following means.

• (1) An image recording material having at least on a surface side of a support a thermosensitive recording element containing a scale-like silver salt of an organic acid, a reducing agent for silver ions and a binder, or a photosensitive recording element containing a scale-like silver salt of an organic acid, a reducing agent for silver ions, a photosensitive silver halide and a binder in which the NH ₄ ⁺ content of all the layers on the surface side of the support having the thermosensitive or photosensitive member is 0.06-3.4 mmol as the coated amount per m ^{2 of} the support ,
• (2) An image-recording material comprising at least on one surface side of a support a thermosensitive recording element containing: a scale-like silver salt of an organic acid, wherein the term "scale-like silver salt of organic acid" means a silver salt of an organic acid having a shape approximating is a rectangular parallelepiped, and if the sides of the rectangular parallelepiped are assumed to be a, b and c starting from the shortest ones (c can be equal to b), x is calculated from the shorter numerical values a and b as follows: x = b / a x is obtained for about 200 particles by the above equation, and when the average value is taken as x (average), those are considered as scale-like particles satisfying the relationship x (average)> 1.5, a reducing agent for silver ion and a binder, or a photosensitive recording element comprising: a scale-like silver salt of an organic acid, a silver ion reducing agent, photosensitive silver halide and a binder, wherein the alkali metal ion content of all the layers on the surface side of the support having the thermosensitive or photosensitive recording element, 0.05-3.6 mmol as coating amount per m ^{2 of} the carrier.
• (3) The material as described above in (1) and (2), wherein the ratio of the contents of alkali metal ion and NH ₄ ⁺ as the molar ratio of (NH ₄ ⁺ ) / (alkali metal ion) is 0.01-30.
• (4) The material as described in (1) or (3) above, wherein the NH ₄ ⁺ content is 0.55-2.8 mmol as the coated amount per m ^{2 of} the carrier.
• (5) The material as described above in (2) or (3), wherein the alkali metal ion content is 0.59-3.0 mmol as the coated amount per m ^{2 of} the carrier.
• (6) The material as described above in (2), (3) and (5), wherein the alkali metal ion is Li ⁺ , Na ⁺ or K ⁺ .
• (7) The material as described in (3) above, wherein the ratio of (NH ₄ ⁺ ) / (alkali metal ion) is 0.1-20.
• (8) The material as described in (3) above, wherein the ratio of (NH ₄ ⁺ ) / (alkali metal ion) is 0.5-5.
• (9) The material as described in any one of (1) to (8) above, wherein the layer containing a scale-like silver salt of an organic acid further contains a phthalic acid compound represented by formula (I):
  
  wherein R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a monovalent substituent; L ₁ and L ₂ each represent a linking group; n1 and n2 are each 0 or 1; M represents a hydrogen atom or a counterion; and k represents a valence of M, and when M represents a hydrogen atom, k is 1, provided that when M represents a hydrogen atom and n1 and n2 are each 0, R ₁ , R ₂ , R ₃ and R _{4 are} not all a hydrogen atom are.
• (10) The material as described in (9) above, wherein M in formula (I) represents an ammonium ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a zinc ion, an ionic polymer, an opposite charge organic compound or a metal complex ion.
• (11) The material as described above under any of (1) to (10), wherein the silver behenate content of the organic acid silver salt is 92 mol% or more.
• (12) The material as described above under any one of (1) to (11), wherein the layer containing the scale-like silver salt of an organic acid is formed by coating a coating solution, wherein 30% by weight or more of the solvent is water , and then drying, and the main binder of this layer is a polymer having an equilibrium moisture content at 25 ° C, 60% RH of 2% by weight or less.
• (13) The material as described above under any of (1) to (12), wherein the material contains a photosensitive recording element.
• (14) The material as described in the above (13), wherein the material has two or more constituent layers containing the photosensitive member on the same surface side of the support on which the photosensitive member is provided, and these two or more constituent layers are simultaneously piled up ,

BRIEF DESCRIPTION OF THE DRAWINGS:

1 Fig. 12 is a schematic cross-sectional view showing an example of a heat developing unit in a plate heating system for use in the present invention;

2 Fig. 12 is a schematic cross-sectional view showing another example of a heat development unit in a plate heating system for use in the invention.

18

Heat generation unit

120

Heating plate

122

pressure roller

130

drive roller

DETAILED DESCRIPTION THE INVENTION:

The The present invention will be described in detail below.

The photothermographic material of the present invention contains a scale-like silver salt of an organic acid, a silver ion reducing agent and a binder at least on one surface side of the support, and contains NH ₄ ⁺ in an amount in all layers on the surface side of the support containing the above components from 0.06 to 3.4 mmol as the coating amount per m ² of the support, or contains alkali metal ions in a total amount in all layers on the surface side of the support containing the above components, from 0.05 to 3.6 mmol as the coating amount per m ^{2 of} the carrier. By using such a flaky silver salt of an organic acid and a prescribed amount of NH ₄ ⁺ or alkali metal ions, a lower silver tint difference is generated by the heat development conditions, and as a result, good silver tone can be obtained by any heat development conditions, whereby a photothermographic material can be obtained shows less variation in photographic properties due to the storage of a coated mass product. In contrast, when a needle-shaped silver salt of an organic acid is used, not only the storage stability decreases, but also the silver tone is deteriorated. On the other hand, if the amounts of NH ₄ ⁺ or alkali metal ion are below the above range, neither the silver tone is improved nor the storage stability is sufficient. When the amounts of NH ₄ ⁺ or alkali metal ion are larger than the above range, on the other hand, the storage stability is lowered.

Further, it is also preferable that both NH ₄ ⁺ and an alkali metal ion are contained so as to obtain preferable silver tone and storage stability, and the ratio of (NH ₄ ⁺ ) / (alkali metal ion) is 0.1-20.

According to the invention, preferably Li ⁺ , Na ⁺ or K ^{+ are used} as the alkali metal ion.

In the present invention, NH ₄ ⁺ and an alkali metal ion may be added as an alkaline solution such as NH ₄ OH, alkali hydroxide metal ions (eg, LiOH, NaOH, KOH), or may be added in the form of a salt formed with an acid, and alternatively For example, they may be added as a salt formed with other photographically useful substances.

These Compounds are added to the coating solution of a layer on the same surface side of the carrier is stacked, as the layer containing a silver salt of an organic Contains acid. If they as an alkaline solution are added, a solution of 0.1-40% by weight is preferably used, and when added in the form of a salt, may be any one selected from a solution a powder and a solid, finely divided dispersion become.

The addition amount of NH ₄ ⁺ is 0.06-3.4 mmol / m ² , preferably 0.55-2.8 mmol / m ² , and the addition amount of an alkali metal ion is 0.05-3.6 mmol / m ² , preferably 0.59-3.0 mmol / m ² . NH ₄ ^{+ may be used} alone or an alkali metal ion alone, but they are preferably used in combination with each other, and in this case, the addition amount is 0.11-7.0 mmol / m ² , preferably 1.14-6.4 mmol / m ² . The ratio of (NH ₄ ⁺ ) / (alkali metal ion) in this case is 0.01-30, preferably 0.1-20 and more preferably 0.5-5.

NH ₄ ⁺ and an alkali metal ion may be added to any layer selected from a layer containing a silver salt of an organic acid, a photosensitive layer, an intermediate layer or a protective layer, and may be added to two or more layers.

Further it is preferable that it thereby becomes a photosensitive layer be added to the main binder of a photosensitive Layer can be added later or as a dicarboxylic acid salt used as a tinting agent used later as well is described.

The layer containing a silver salt of an organic acid (an image-recording layer) of the photothermographic material of the present invention can be prepared by coating an aqueous system with an environmentally friendly coating solution in which 30% by weight or more of the solvent is formed by water, and it is preferable to a polymer having an equilibrium moisture content at 25 ° C and 60% relative humidity of 2% by weight or less, which is preferred for obtaining good photographic properties as a main binder of this layer. The invention A suitable photothermographic material preferably comprises a photosensitive layer containing a photosensitive silver halide and provided on the same surface side of the support as the layer containing a silver salt of an organic acid. It is particularly preferable that the layer containing the silver salt of an organic acid contains a photosensitive silver halide. From the viewpoint of production, it is also preferable to use a hydrophilic binder as a main binder of the constitutional layers such as an intermediate layer and the protective layer provided on the same surface side as the layer containing the silver salt of the organic acid (preferably the photosensitive layer) , and the layer containing the silver salt of an organic acid is coated simultaneously with these layers.

Usable according to the invention photo-insensitive silver salts of an organic acid scale-like and they are preferably in a photosensitive Layer or a photo-insensitive layer included. organic acids for the production of silver salts are preferably long-chain fatty acids, preferably 10-30 carbon atoms and more preferably 10-15 carbon atoms exhibit. It can too organic silver salt complexes are used. The ligands of Complexes preferably have an overall stability constant across from Silver ions of 4.0-10.0. Organic silver salt are in Research Disclosure, No. 17029 and ibid. No. 29963.

Examples for organic Silver salts include silver salts of fatty acids (e.g., gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid), silver salts carboxyalkylthioureas (e.g., 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea) Silver complexes of polymerization reaction products of aldehydes (e.g., formaldehyde, acetaldehyde, butyraldehyde) with hydroxy-substituted aromatic carboxylic acids, Silver salts of aromatic carboxylic acids (e.g., salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid) Silver salts or silver complexes of thioen (e.g., 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene, 3-carboxymethyl-4-thiazoline-2-thioene), silver salts or silver complexes of nitrogen acids (e.g., imidazole, pyrazole, urazole, 1,2,4-thiazole, 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole, Benzotriazole), silver salts of saccharin, 5-chlorosalicylaldoxime silver salt and mercaptide silver salts one.

According to the invention scale-like silver salts of organic acids are selected from these compounds. It is preferable to use only flaky silver salts of organic acids as organic silver salts, but the above organic silver salts may also be used in combination with silver salts of organic acids when the amount is in the range of 30 wt% or less of the total amount. Fatty acid silver salts are preferred as silver salts of an organic acid, especially silver salts of an organic acid, which have 92 mol% or more of silver behenate, and most preferred is silver behenate. The silver salts of an organic acid are preferably used in an amount of 0.05-3 g / m ² , more preferably 0.3-2 g / m ² , based on the amount of silver.

With respect to the scale-like silver salt of an organic acid used in the present invention, the property "scale-like" is evaluated as follows. A silver salt of an organic acid is observed by an electron microscope, the shape of the particle of the silver salt of the organic acid is approximated to a rectangular parallelepiped, and if the sides of the rectangular parallelepiped as a, b, and c, starting with the shortest side (c can b), x is calculated from the smaller numerical values a and b as follows: x = b / a x is determined for about 200 particles according to the above equation, and when the average value is taken as x (average), those satisfying the relationship x (average)> 1.5 are regarded as scale-like particles, preferably at 30> x (Average)> 1.5, more preferably 20> x (average)> 2.0. In this connection, acicular is 1 <x (average) <1.5.

at a flaky particle may be a as the thickness of a tabular particle be viewed, that is an area in which b and c represent the sides of the main surface. The average value of a is preferably 0.01-0.23 μm, and more preferably 0.1-0.20 μm. The average value of c / b is preferably 1-6, farther preferably 1.05-4, more preferably 1.1-3, and most preferably 1.1-2.

When an aqueous solution containing a water-soluble silver salt and an aqueous solution of a tertiary alcohol containing an alkali metal salt of an organic acid in a reaction vessel with are reacted with each other (including the step of adding the aqueous solution of a tertiary alcohol containing an alkali metal salt of an organic acid to the solution in the reaction vessel), a flaky silver salt of an organic acid is preferably formed by the temperature difference between the solution in the Reaction vessel (preferably, the aqueous solution containing a water-soluble silver salt is added in advance to the reaction vessel or when the aqueous solution containing a water-soluble silver salt is not preliminarily added but simultaneously with the aqueous solution of a tertiary alcohol containing an alkali metal salt contains an organic acid, is added from the former, the solution in the reaction vessel is water or a mixed solvent of water and a tertiary alcohol, as described later, and further, even if the aqueous solution, the egg n water-soluble silver salt is added in advance into the reaction vessel, water or a mixed solvent of water and a tertiary alcohol are added in advance to the reaction vessel) and the aqueous solution of a tertiary alcohol containing an alkali metal salt of an organic acid to the reaction vessel is added, adjusted to 20-85 ° C. By maintaining the temperature difference during the addition of the aqueous solution of a tertiary alcohol containing an alkali metal salt of an organic acid, the crystal form of the silver salt of the organic acid can be controlled favorably.

When this water-soluble Silver salt is preferred silver nitrate, and as the concentration of water-soluble Silver salt in the aqueous solution 0.03-6.5 mol / l is preferred, and more preferably 0.1-5 mol / l, and the pH of the aqueous solution is preferably 2-6, more preferably 3.5-6.

In the aqueous Solution, the one water-soluble Contains silver salt, can be a tertiary Alcohol containing 4-6 carbon atoms, and in this Case is the content of the tertiary Alcohol 70 vol.% Or less, preferably 50 vol.% Or less, based on the total volume of the aqueous solution containing a water-soluble Contains silver salt. The temperature of the solution is preferably 0-50 ° C, more preferably 5-30 ° C. If the watery Solution, the one water-soluble Contains silver salt, simultaneously with the aqueous solution of a tertiary Alcohol containing an alkali metal salt of an organic acid added is, is the temperature is preferably 5-15 ° C, how later described.

The Alkali metal of the alkali metal salt of the organic acid especially Na or K. The alkali metal salt of the organic acid becomes prepared by adding NaOH or KOH to an organic acid. It is preferable, the weight of the alkali to an equivalent amount or less the weight of the organic acid at this time, reducing unreacted organic Acid remains. The remaining organic acidity at this time is 3-50 mol%, preferably 3-30 mol%, per mol of the total amount organic acid. Further, alkali is added in an amount that is larger than the prescribed amount, and the excess amount of alkali can then by adding an acid, such as nitric acid or sulfuric acid, be neutralized.

Furthermore The pH may be due to the required properties of the silver salt the organic acid be set. For pH adjustment, any acids and Alkalis are used.

To the aqueous Solution, the one water-soluble Contains silver salt, the aqueous solution a tertiary Alcohol containing an alkali metal salt of an organic acid, or to the solution in the reaction vessel For example, a compound of the formula (I) as disclosed in JP-A-62-65035 (the term "JP-A" as used herein) is meant to be an "unaudited published Japanese Patent Application), an N-heterocyclic compound having a water-soluble Group as disclosed in JP-A-62-150240, an inorganic peroxide, as disclosed in JP-A-50-101019, a sulfur compound as in JP-A-51-78319 discloses a disulfide compound as disclosed in JP-A-57-643 disclosed or a hydrogen peroxide may be added.

The aqueous solution of a tertiary alcohol containing an alkali metal salt of an organic acid according to the present invention is preferably a mixed solvent of a tertiary alcohol having 4-6 carbon atoms and water, thereby obtaining the homogeneity of the solution. If the carbon atom number exceeds this range, the compatibility with water is deteriorated, which is not advantageous. Among the tertiary alcohols of 4-6 carbon atoms, t-butanol, which is most compatible with water, is most preferred. Since alcohols other than tertiary alcohols have reducibility, unfavorable influences on formation of the metal salt of the organic acid are caused as described above. The content of the tertiary alcohol contained in the aqueous solution of a tertiary alcohol containing an alkali metal salt of an organic acid is 3-70%, preferably 5-50% by volume of the solvent based on the volume of the water content in the aqueous solution of the tertiary alcohol.

The Concentration of the alkali metal salt of organic acids in the aqueous solution a tertiary Alcohol containing an alkali metal salt of an organic acid, such as inventively usable, is 7-50% by weight, preferably 7-45% by weight, and more preferably 10-40 % By weight, based on the weight ratio.

The Temperature of the aqueous solution a tertiary Alcohol containing an alkali metal salt of an organic acid, the to the reaction vessel is added is preferably 5-90 ° C, more preferably 60-85 ° C, and most preferably 65-85 ° C, for the purpose of maintaining the required temperature for Prevention of phenomena such as crystallization and solidification of the alkali metal salt of the organic Acid. The temperature is preferably at a certain temperature, which is selected within the above range over the entire duration of the reaction controlled.

The invention Silver salt of an organic acid is prepared by (i) the process wherein the total amount the aqueous Solution, the one water-soluble Contains silver salt, in advance into the reaction vessel is added, and then the aqueous solution of a tertiary alcohol, containing an alkali metal salt of an organic acid added thereto (a single addition method), or (ii) the process wherein the aqueous solution is a water-soluble Contains silver salt, and the watery solution a tertiary alcohol, which contains an alkali metal salt of an organic acid, simultaneously over at least be added for a certain period of time (a simultaneous addition procedure). The latter simultaneous addition method according to the invention for the control the average particle size of the silver salt of the organic Acid and for producing a narrow particle size distribution, preferably applied. In this case, preferably 30 vol.% Or more, more preferably 50-75 vol.%, the total amount added simultaneously added. If one of the two solutions is added in advance, is preferably the aqueous Solution, the one water-soluble Contains silver salt, first added.

In In any case, the temperature of the solution in the reaction vessel (the pre-added aqueous solution, the a water-soluble Contains silver salt, or if the watery Solution, the one water-soluble silver salt contains is not pre-added, the solvent, the advance in the reaction vessel preferably 5-75 ° C, more preferably 5-60 ° C and on most preferably 10-50 ° C. The temperature is preferably over the entire reaction a certain temperature selected within the above range However, it is also preferable to set the temperature in certain Pattern within the above range.

According to the invention, the temperature difference between the watery solution a tertiary Alcohol containing an alkali metal salt of an organic acid, and the solution in the reaction vessel preferably 20-85 ° C, more preferably 30-80 ° C. In this case, it is preferable that the temperature of the aqueous solution a tertiary Alcohol containing an alkali metal salt of an organic acid is higher as that of the solution in the reaction vessel.

On This way the speed of the crystallite precipitation can be the aqueous Solution of a tertiary Alcohol containing an alkali metal salt of an organic acid with a high temperature as a result of the sudden quenching in the reaction vessel, and the rate of conversion to a silver salt of an organic Acid through the reaction with the water-soluble Silver salt can be controlled in a preferred manner. As a result, the Crystal shape and the crystal size of the silver salt of the organic acid and the crystal size distribution be controlled in a preferred manner. At the same time, the Properties of the photothermographic material, in particular of the photothermographic photosensitive material further improved become.

advance can be a solvent in the reaction vessel be given, e.g. is preferably water as a solvent which is added in advance, and also is preferable a mixed solvent from a tertiary Alcohol used with water.

According to the invention a dispersing aid which is soluble in an aqueous medium, to the aqueous solution a tertiary Alcohol containing an alkali metal salt of an organic acid, and the aqueous Solution, the one water-soluble Contains silver salt, or to the reaction solution be added. As a dispersion aid, any Compound used as long as they formed the silver salt an organic acid can disperse. Specific examples correspond to the dispersing aids for silver salts organic acids, how later described.

In the manufacturing process for the inventive Silver salt of an organic acid it is preferable to after the desalting / dehydration process to carry out the silver salt formation. Procedure for desalting / dehydration is not particularly limited and it can well-known conventional Be applied. For example, preferably, generally known filtration methods, such as centrifugal filtration, Suction filtration, ultrafiltration and washing by agglomeration formed flakes are applied. The distance of the supernatant by centrifugal separation precipitation is also preferably used. Desalting / dehydration can be repeated only once or several times. The addition and removal of water can be continuous or separate carried out become. The desalting / dehydration is carried out until the conductivity the dehydration water finally a value of 300 μS / cm or less, more preferably 100 μS / cm or less, and most preferably reaches 60 μS / cm or less. The lower limit of conductivity is not particularly limited in this case, but is generally about 5 μS / cm.

Further can be used to improve the coating surface condition of a photothermographic material, in particular a photothermographic photosensitive material, preferably an aqueous dispersion a silver salt of an organic acid, the resulting dispersion exposed to high pressure and flow velocity and redissolving by pressure release, whereby a finely divided water dispersion is obtained. This here The dispersion medium used is preferably only water, however can be an organic solvent contained when the amount is 20 wt.% or less.

One Silver salt of an organic acid can be finely dispersed in the presence of a dispersing aid using well-known dispersing devices (e.g. a high speed mixer, a homogenizer, a High Speed Turbo Mill, a Banbury mixer, a homomixer, a kneader, a ball mill, a vibrating ball mill, a Planetary ball mill, an attritor, a sand mill, a ball mill, a colloid mill, a jet mill, a roller mill, a drum and a high-speed stone mill).

to Obtaining fine particles of a silver salt of an organic acid with a small particle size and without agglomeration which can be used according to the invention inventively a method for obtaining a finely divided solid dispersion used with a dispersant. After the aqueous dispersion a silver salt of an organic acid obtained by the process according to the invention was brought to high pressure / high flow rate is preferably a process of redispersing the dispersion applied by pressure drop.

If further during dispersing a photosensitive silver salt together with the silver salt of organic acid is present, the fog increases and the sensitivity increases takes off extremely. Therefore, it is further preferred that substantially contain no photosensitive silver salt in the aqueous dispersion solution is. The content of the aqueous dispersion solution to be dispersed is 0.1 mol% or less per mol of silver salt of the organic acid in the Solution, wherein the addition of a photosensitive silver salt is preferably not done becomes.

Feststoffdispergiervorrichtungen and techniques for carrying out the aforementioned dispersion are detailed in, for example, Toshio Kajiuchi, Hiroshi Usui, Rheology of Dispersion System and Techniques of Dispersion, pages 357-403, Shinoyama Publishing Co., Ltd. (1991), Advancement of Chemical Engineering, the 24th Series, Pages 184 and 185, compiled by Tokai Branch of the Chemical Engineering Society, published Maki Shoten (1990), JP-A-59-49832, U.S. Patent 4,533,254, JP-A-8-137044, JP-A-8-238848, JP-A-2-261525, JP-A-1-94933 and so on. The invention Redispersion method is a method wherein an aqueous dispersion solution, the containing at least one silver salt of an organic acid by high pressure using a high pressure pump and the like introduced into a piping system, by passed through a fine slot in the pipeline and then the to the dispersion solution applied pressure suddenly is discharged, whereby a fine dispersion is effected.

As a reason that the dispersion of the fine particles can be brought about by using a high-pressure homogenizer, dispersion forces are considered, such as (a) the "shearing force" generated when a dispersoid passes through a narrow gap at high pressure and high speed and (b) the "cavitation force" produced when the dispersoid is released from high pressure to atmospheric pressure. As a dispersing apparatus of this type, a Gaulin homogenizer in which a high-pressure dispersoid is made to flow at a high speed in a narrow gap on a cylindrical surface has hitherto been used, the dispersoid by this force impacted on the surrounding walls, and this impact force causes emulsification and dispersion. The applied pressure is generally in the range of 100-600 kg / cm ² and the flow rate is several meters to 30 m / sec, and various means have been developed to increase the dispersion efficiency, such as the provision of blade blades in high flow velocity zones, thereby increasing the number the impact is increased. On the other hand, devices have been developed which make it possible to realize a dispersion at higher pressure and higher flow rate. As representative examples, there are exemplified a microfluidizer (manufactured by Micro Fluidex International Corp.) and a nanomizer (manufactured by Tokusho Kika Kogyo Co., Ltd.).

According to the invention, it is possible to adjust the dispersion of the silver salt of the organic acid in the desired particle size by adjusting the flow rate, the differential pressure at the time of pressure drop, and the number of processings. From the viewpoint of the photographic properties and the particle size, the flow rate is preferably 200-600 m / sec, more preferably 300-600 m / sec, and the pressure drop differential pressure is preferably 900-3000 kg / cm ² , more preferably 1.500-3000 kg / cm ² . The number of times of the dispersion processing may be selected depending on need, and is generally 1-10 times, but preferably 1-3 times or so in view of productivity. From the viewpoint of dispersion properties and photographic properties, it is not preferable to keep the temperature of an aqueous dispersion solution high under high pressure, and when the temperature exceeds 90 ° C, the particle size tends to increase, and further fogging tends to increase , Thus, according to the present invention, it is preferable to include a cooling process in the steps before conversion to high pressure / high flow rate, pressure drop or both, whereby the temperature of the aqueous dispersion is 5-90 ° C, more preferably 5-80 ° C , and more preferably 5-65 ° C is maintained. In particular, it is effective to provide such a cooling process during high-pressure dispersion at 1,500-3,000 kg / cm ² . A cooling device may be arbitrarily selected from, for example, a double pipe and a triple pipe using a static mixer, a multi-tube heat exchanger and a wound heat exchanger, depending on the required heat exchange amount. Further, in order to increase the heat exchange efficiency, it is necessary to appropriately select the diameter, the thickness and the material of the pipe in consideration of the pressure. As the cooling medium in the condenser, depending on the heat exchange amount, spring water of 20 ° C, cooled water of 5-10 ° C treated with a refrigerator or, if necessary, a cooling medium such as ethylene glycol / water of -30 ° C be used.

If a fine solid particle atomization of a silver salt of a organic acid is carried out using a dispersant, can in any way the following dispersants are selected e.g. synthetic anionic polymers such as polyacrylic acid, acrylic acid copolymers, Maleic acid copolymers, Maleic acid copolymers and acryloylmethylpropane-sulfonic acid copolymers, semi-synthetic anionic polymers such as carboxymethyl starch and Carboxymethylcellulose, anionic polymers, such as alginic acid and pectinic acid, anionic surfactants as disclosed in JP-A-52-92716 and WO 88/04794, Compounds disclosed in JP-A-7-350753 are well known anionic, nonionic and cationic surfactants, others in general known polymers, such as, for example, polyvinyl alcohol, polyvinylpyrrolidone, Carboxymethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose, and natural high molecular weight compounds such as gelatin. In general, a dispersing aid with the powder of Silver salt of an organic acid or a silver salt of an organic acid in a wet cake-like state mixed before dispersion and as a slurry in a dispersing device introduced. Alternatively, a dispersing aid may be pre-treated with a silver salt an organic acid mixed and a heat treatment or subjected to a treatment with a solvent and then to a powder or wet cake of the silver salt of the organic Acid processed become. The pH adjustment may be before, after or during the Dispersion can be carried out with a suitable pH adjusting agent.

In addition to the mechanical dispersion, the silver salt of the organic Acid by pH control in a solvent coarsely dispersed and then by changing the pH in the presence be atomized a dispersing aid. At this time can be an organic solvent for one coarse dispersion and the organic solvent is generally removed after the termination of atomization.

The prepared dispersion may be preserved under agitation or in a high-viscosity state with a hydrophilic colloid (for example, in a gel state using gelatin) for the purpose of preventing precipitation of fine particles during preservation. Furthermore, it is be It is preferable to add preservatives to inhibit the proliferation of various bacteria.

The according to the invention Manufacturing process for the silver salt of an organic acid prepared silver salt an organic acid is preferably in an aqueous solvent dispersed, with an aqueous Photosensitive silver salt solution mixed and as a coating solution for a photosensitive delivered imaging medium.

Examples preferred for the invention Reducing agents used include phenidone, hydroquinone, catechol and hindered phenol. In terms of of the reducing agent is disclosed in U.S. Patents 3,770,448, 3,773,512, 3 593 867, 4 460 681 and Research Disclosure, Nos. 17029 and ibid. No. 29963.

specific examples for Reducing agents include an aminohydrocycloalkenone compound (e.g., 2-hydroxypiperidine-2-cyclohexenone), an N-hydroxyurea derivative (e.g., N-p-methylphenyl-N-hydroxyurea), Aldehyde or ketone hydrazones (e.g., anthracene aldehyde phenylhydrazone), Phosphoramidophenols, phosphoramidoanilines, polyhydroxybenzenes (e.g. Hydroquinone, t-butylhydroquinone, isopropylhydroquinone, 2,5-dihydroxyphenylmethylsulfone), Sulfohydroxaminsäuren (e.g., benzenesulfohydroxamic acid), Sulfonamidoanilines (e.g., 4- (N-methanesulfonamido) anilines), 2-tetrazolylthiohydroquinones (e.g., 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone), Tetrahydroquinoxalines (e.g., 1,2,3,4-tetrahydroquinoxaline), amidoxins, Combinations of azines (e.g., aliphatic carboxylic acid aryl hydrazides) with ascorbic acid, Combinations of polyhydroxybenzene hydroxylamine, reductone, hydrazine, hydroxamic acids, Combinations of azines with sulfonamidophenols, an a-cyanophenylacetic acid derivative, Combinations of bis-β-naphthol with a 1,3-dihydroxybenzene derivative, 5-pyrazolones, sulfonamidophenols, 2-phenylindane-1,3-dione, chroman, 1,4-dihydropyridine (e.g., 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine), Bisphenols (e.g., bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol, 2,4-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (2-hydroxy-3,5-dimethylphenyl), 3,5,5-trimethylhexane, 4,4-ethylidene bis (2-t-butyl-6-methyl) phenol, UV-sensitive ascorbic acid derivatives and 3-pyrazolidones.

ester of aminoreductones which act as reductant precursors (e.g., piperidinohexose reductone monoacetate) can be used as a reducing agent become.

One particularly preferred reducing agent is hindered phenol.

The addition amount of the reducing agent is preferably 0.01-5.0 g / m ² , more preferably 0.1-3.0 g / m ² .

The invention photothermographic material comprises a support having a layer provided thereon, which has a scale-like silver salt of an organic acid (i.e., an image-forming layer); and the one reducing agent for a Containing silver ion and a binder, and preferably a phthalic acid compound of formula (I) on the same surface side of the support which applies the layer containing a silver salt of an organic acid is. The inventive Photothermographic material is preferably a photothermographic Photosensitive material containing a photosensitive silver halide on the same surface side of the carrier as the layer containing a silver salt of an organic acid has. Particularly preferably contains the layer containing a silver salt of an organic acid Photosensitive silver halide. Even more preferred is also a reducing agent for silver ions contained in the same layer. In this photothermographic Photosensitive material is made by using a scale-like Silver salt of an organic acid as the silver salt of an organic acid and a phthalic acid compound of the formula (I) has a smaller silver tint difference by the heat development conditions and as a result, good silver tone can be generated by any heat development conditions to obtain a photothermographic material which can be less variance of photographic properties can show the storage. In contrast, then, if one acicular Silver salt of an organic acid not only reduces storage stability, but also the silver tint deteriorated. On the other hand, if a connection such as a phthalic acid, that of the phthalic acid compound of the formula (I) is different, is used alone especially the silver tint deteriorated.

In order to improve the storage stability, silver salts of an organic acid containing 92 mol% or more of a silver behenate are preferably used. Further, the layer containing the silver salt of the organic acid may be formed by an aqueous coating system with an environmentally friendly coating solution in which 30% by weight or more of the solvent is formed by water, and it is preferable to use a polymer having an equilibrium moisture content at 25 ° C and 60 rela 2% by weight or less, which is preferred for obtaining good photographic properties, as the main binder of this layer. From the viewpoint of production, it is further preferable to use a hydrophilic binder as a main binder of the intermediate layer and the protective layer provided on the same surface side as the layer containing the silver salt of an organic acid layer, and the layer containing the silver salt of the organic acid is piled up at the same time as these build-up layers.

worin R₁, R₂, R₃ und R₄ jeweils ein Wasserstoffatom oder einen monovalenten Substituenten darstellen; n1 und n2 repräsentieren jeweils 0 oder 1; M ist ein Wasserstoffatom oder ein Gegenion, mit der Massgabe, dass wenn M ein Wasserstoffatom ist und n1 und n2 jeweils 0 sind, R₁, R₂, R₃ und R₄ nicht alle ein Wasserstoffatom darstellen. Beispiele für monovalente Substituenten, die durch R₁, R₂, R₃ und R₄ repräsentiert werden, schliessen eine Alkylgruppe (vorzugsweise eine Alkylgruppe mit 1-20, weiter bevorzugt 1-12 und besonders bevorzugt 1-8 Kohlenstoffatomen, z.B. Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, t-Butyl, n-Octyl, n-Decyl, n-Hexadecyl, Cyclopropyl, Cyclopentyl, Cyclohexyl), eine Alkenylgruppe (vorzugsweise eine Alkenylgruppe mit 2-20, weiter bevorzugt 2-12 und besonders bevorzugt 2-8 Kohlenstoffatomen, z.B. Vinyl, Allyl, 2-Butenyl, 3-Pentenyl), eine Alkinylgruppe (vorzugsweise eine Alkinylgruppe mit 2-20, weiter bevorzugt 2-12 und besonders bevorzugt 2-8 Kohlenstoffatomen, z.B. Propargyl, 3-Pentinyl), eine Arylgruppe (vorzugsweise eine Arylgruppe mit 6-30, weiter bevorzugt 6-20 und besonders bevorzugt 6-12 Kohlenstoffatomen, z.B. Phenyl, p-Methylphenyl, Naphthyl), eine Aminogruppe (vorzugsweise eine Aminogruppe mit 0-20, weiter bevorzugt 0-10 und besonders bevorzugt 0-6 Kohlenstoffatomen, z.B. Amino, Methylamino, Dimethylamino, Dibenzylamino), eine Alkoxylgruppe (vorzugsweise eine Alkoxylgruppe mit 1-20, weiter bevorzugt 1-12 und besonders bevorzugt 1-8 Kohlenstoffatomen, z.B. Methoxy, Ethoxy, Butoxy, Benzyloxy), eine Aryloxygruppe (vorzugsweise eine Aryloxygruppe mit 6-20, weiter bevorzugt 6-16 und besonders bevorzugt 6-12 Kohlenstoffatomen, z.B. Phenyloxy, 2-Naphthyloxy), eine Acylgruppe (vorzugsweise eine Acylgruppe mit 1-20, weiter bevorzugt 1-16 und besonders bevorzugt 1-12 Kohlenstoffatomen, z.B. Acetyl, Benzoyl, Formyl, Pivaloyl), einen Alkoxycarbonylgruppe (vorzugsweise eine Alkoxycarbonylgruppe mit 2-20, weiter bevorzugt 2-16 und besonders bevorzugt 2-12 Kohlenstoffatomen, z.B. Methoxycarbonyl, Ethoxycarbonyl, Tetradecyloxycarbonyl), eine Aryloxycarbonylgruppe (vorzugsweise eine Aryloxycarbonylgruppe mit 7-20, weiter bevorzugt 7-16 und besonders bevorzugt 7-10 Kohlenstoffatomen, z.B. Phenyloxycarbonyl), eine Aryloxygruppe (vorzugsweise eine Aryloxygruppe mit 2-20, weiter bevorzugt 2-16 und besonders bevorzugt 2-10 Kohlenstoffatomen, z.B. Acetoxy, Benzoyloxy), eine Acylaminogruppe (vorzugsweise eine Acylaminogruppe mit 2-20, weiter bevorzugt 2-16 und besonders bevorzugt 2-10 Kohlenstoffatomen, z.B. Acetylamino, Propionylamino, Benzoylamino), eine Alkoxycarbonylaminogruppe (vorzugsweise eine Alkoxycarbonylaminogruppe mit 2-20, weiter bevorzugt 2-16 und besonders bevorzugt 2-12 Kohlenstoffatomen, z.B. Methoxycarbonylamino), eine Aryloxycarbonylaminogruppe (vorzugsweise eine Aryloxycarbonylaminogruppe mit 7-20, weiter bevorzugt 7-16 und besonders bevorzugt 7-12 Kohlenstoffatomen, z.B. Phenyloxycarbonylamino), eine Sulfonylaminogruppe (vorzugsweise eine Sulfonylaminogruppe mit 1-20, weiter bevorzugt 1-16 und besonders bevorzugt 1-12 Kohlenstoffatomen, z.B. Methansulfonylamino, Octansulfonylamino, Benzolsulfonylamino), eine Sulfamoylgruppe (vorzugsweise eine Sulfamoylgruppe mit 0-20, weiter bevorzugt 0-16 und besonders bevorzugt 0-12 Kohlenstoffatomen, z.B. Sulfamoyl, Methylsulfamoyl, Dimethylsulfamoyl, Phenylsulfamoyl), eine Carbamoylgruppe (vorzugsweise eine Carbamoylgruppe mit 1-20, weiter bevorzugt 1-16 und besonders bevorzugt 1-12 Kohlenstoffatomen, z.B. Carbamoyl, Methylcarbamoyl, Diethylcarbamoyl, Phenylcarbamoyl), eine Alkylthiogruppe (vorzugsweise eine Alkylthiogruppe mit 1-20, weiter bevorzugt 1-16 und besonders bevorzugt 1-12 Kohlenstoffatomen, z.B. Methylthio, Ethylthio), eine Arylthiogruppe (vorzugsweise eine Arylthiogruppe mit 6-12, weiter bevorzugt 6-16 und besonders bevorzugt 6-12 Kohlenstoffatomen, z.B. Phenylthio), eine Sulfonylgruppe (vorzugsweise eine Sulfonylgruppe mit 1-20, weiter bevorzugt 1-16 und besonders bevorzugt 1-12 Kohlenstoffatomen, z.B. Mesyl, Tosyl), eine Sulfinylgruppe (vorzugsweise eine Sulfinylgruppe mit 1-20, weiter bevorzugt 1-16 und besonders bevorzugt 1-12 Kohlenstoffatomen, z.B. Methansulfinyl, Benzolsulfinyl), eine Ureidogruppe (vorzugsweise eine Ureidogruppe mit 1-20, weiter bevorzugt 1-16 und besonders bevorzugt 1-12 Kohlenstoffatomen, z.B. Ureido, Methylureido, Phenylureido), eine Phosphorsäureamidgruppe (vorzugsweise eine Phosphorsäureamidgruppe mit 1-20, weiter bevorzugt 1-16 und besonders bevorzugt 1-12 Kohlenstoffatomen, z.B. Diethylphosphorsäureamid, Phenylphosphorsäureamid), eine Hydroxylgruppe, eine Carboxylgruppe, eine Sulfogruppe, eine Sulfinogruppe (eine Sulfinsäuregruppe), eine Mercaptogruppe, ein Halogenatom (z.B. Fluor, Chlor, Brom, Iod), eine Cyanogruppe, eine Nitrogruppe, eine Hydroxamsäuregruppe, eine Hydrazinogruppe und eine heterocyclische Gruppe (z.B. Imidazolyl, Pyridyl, Furyl, Piperidyl, Morpholino) ein. Ein Substituent, der mit z.B. einem Alkalimetall ein Salz bilden kann, kann ein Salz bilden. Diese Substituenten können ferner substituiert sein. Wenn zwei oder mehr Substituenten vorhanden sind, können diese identisch oder unterschiedlich sein.Hereinafter, the phthalic acid compound of the formula (I) will be described in more detail.

wherein R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a monovalent substituent; n1 and n2 each represent 0 or 1; M is a hydrogen atom or a counter ion, R _1, R _2, R ₃ and R ₄ do not represent a hydrogen atom with the proviso that when M is a hydrogen atom, and n1 and n2 are each 0 all. Examples of monovalent substituents represented by R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group (preferably an alkyl group having 1-20, more preferably 1-12 and most preferably 1-8 carbon atoms, eg, methyl, ethyl , n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group (preferably an alkenyl group having 2-20, more preferably 2 -12 and more preferably 2-8 carbon atoms, for example vinyl, allyl, 2-butenyl, 3-pentenyl), an alkynyl group (preferably an alkynyl group having 2-20, more preferably 2-12 and more preferably 2-8 carbon atoms, eg propargyl , 3-pentynyl), an aryl group (preferably an aryl group having 6-30, more preferably 6-20 and more preferably 6-12 carbon atoms, eg phenyl, p-methylphenyl, naphthyl), an amino group (preferably an amino group of 0-20 , more preferably 0-10 and more preferably 0-6 carbon atoms, eg Am ino, methylamino, dimethylamino, dibenzylamino), an alkoxyl group (preferably an alkoxyl group having 1-20, more preferably 1-12 and particularly preferably 1-8 carbon atoms, eg methoxy, ethoxy, butoxy, benzyloxy), an aryloxy group (preferably an aryloxy group with 6-20, more preferably 6-16 and most preferably 6-12 carbon atoms, eg phenyloxy, 2-naphthyloxy), an acyl group (preferably an acyl group having 1-20, more preferably 1-16 and most preferably 1-12 carbon atoms, eg Acetyl, benzoyl, formyl, pivaloyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2-20, more preferably 2-16 and most preferably 2-12 carbon atoms, eg methoxycarbonyl, ethoxycarbonyl, tetradecyloxycarbonyl), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7- 20, more preferably 7-16 and most preferably 7-10 carbon atoms, eg phenyloxycarbonyl), an aryloxy group (preferably an aryloxy group with 2-20, more preferably 2-16 and more preferably 2-10 carbon atoms, eg acetoxy, benzoyloxy), an acylamino group (preferably an acylamino group having 2-20, more preferably 2-16 and more preferably 2-10 carbon atoms, eg acetylamino, propionylamino, benzoylamino), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2-20, more preferably 2-16 and more preferably 2-12 carbon atoms, eg methoxycarbonylamino), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7-20, more preferably 7-16 and most preferably 7-12 Carbon atoms, eg, phenyloxycarbonylamino), a sulfonylamino group (preferably, a sulfonylamino group having 1-20, more preferably 1-16, and particularly preferably 1-12 carbon atoms, eg, methanesulfonylamino, octanesulfonylamino, benzenesulfonylamino), a sulfamoyl group (preferably a sulfamoyl group having 0-20, etc.) preferably 0-16 and particularly preferably 0-12 carbon atoms, for example sulfamoyl, methyls ulfamoyl, dimethylsulfamoyl, phenylsulfamoyl), a carbamoyl group (preferably a carbamoyl group having 1-20, more preferably 1-16 and particularly preferably 1-12 carbon atoms, eg carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl), an alkylthio group (preferably an alkylthio group having 1 to 1 carbon atoms). 20, more preferably 1-16 and particularly preferably 1-12 carbon atoms, for example methylthio, ethylthio), an arylthio group (preferably an arylthio group having 6-12, more preferably 6-16 and more preferably 6-12 carbon atoms, eg phenylthio) Sulfonyl group (preferably a sulfonyl group having 1-20, more preferably 1-16 and particularly preferably 1-12 carbon atoms, for example mesyl, tosyl), a sulfinyl group (preferably a sulfinyl group having 1-20, more preferably 1-16 and particularly preferably 1- 12 carbon atoms, for example methanesulfinyl, benzenesulfinyl), a ureido group (preferably a ureido group having 1-20, more preferably 1-16 and particularly preferably 1-12 carbon enstoffatomen, eg ureido, methylureido, phenylureido), a Phosphorsäureamidgruppe (preferably a Phosphorsäureamidgruppe with 1-20, more preferably 1-16 and particularly preferably 1-12 carbon atoms, for example diethylphosphoric acid amide, phenylphosphoric acid amide), a hydroxyl group, a carboxyl group, a sulfo group, a sulfino group (a sulfinic acid group), a mercapto group, a halogen atom (eg fluorine, chlorine, Bromine, iodine), a cyano group, a nitro group, a hydroxamic acid group, a hydrazino group, and a heterocyclic group (eg, imidazolyl, pyridyl, furyl, piperidyl, morpholino). A substituent which can form a salt with, for example, an alkali metal can form a salt. These substituents may be further substituted. When two or more substituents are present, they may be the same or different.

Preferred examples of the substituents represented by R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an acylamino group, an alkoxycarbonylamino group, a Aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric acid group, hydroxyl group, carboxyl group, sulfo group, sulfino group, sulfonyl group, halogen atom, cyano group, nitro group and heterocyclic group. Further preferred groups include an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an acyl group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a hydroxyl group, a sulfonyl group, a halogen atom and a cyano group, and particularly preferred groups include one Alkyl group, an aryl group, an alkoxyl group and a halogen atom.

R ₁ , R ₂ , R ₃ and R ₄ are each particularly preferably a hydrogen atom or the above-exemplified, particularly preferred substituent.

L ₁ and L ₂ each represent a linking group. L ₁ and L ₂ represented linking groups are preferably divalent connecting groups having 1-6 carbon atoms. Preferred examples include an alkylene group of 1-6 carbon atoms (eg, -CH ₂ -, -CH ₂ CH ₂ -), -C = O-, -CONH-, -SO ₂ NH-, -COO-, -O-, and combinations thereof one. More preferred are alkylene groups having 1-3 carbon atoms, and these may further have a substituent.

n1 and n2 each represent 0 or 1, and preferably, n1 and n2 each represent 0. When n1 and n2 are each 1, L ₁ and L _{2 may be} identical or different.

M is a hydrogen atom or a counterion and k is the valence of M, and when M is a hydrogen atom, k = 1. Examples of counterions include an inorganic or organic ammonium ion (e.g. an ammonium ion, a triethylammonium ion, a pyridinium ion) Alkali metal ion (e.g., a lithium ion, a sodium ion, a potassium ion), an alkaline earth metal ion (e.g., a calcium ion, a barium ion) Magnesium ion) and other ions (e.g., an aluminum ion, a zinc ion) one. As counterions are also ionic polymers, other organic Reverse charge or metal complexation compounds (e.g. a hydroxypentaquaaluminum (III) ion, a tris (2,2'-bipyridine) iron (II) ion). M can form an internal salt with another substituent in the molecule, Preferred examples include a sodium ion, a potassium ion Ammonium ion, a triethylammonium ion and a pyridinium ion, and further preferred are a sodium ion, a potassium ion and a Ammonumion. According to the invention M is preferably a counterion. If there are two groups M, these are generally identical, but they may be different in certain cases.

specific examples for Compounds of formula (I) are given below but are the present invention is not limited thereto.

Ammonium phthalate, sodium phthalate, potassium phthalate, lithium phthalate,

The compound of the formula (I) of the present invention can be synthesized by the methods described in Tetrahedron, Vol. 31 (20), pp. 2607-2619, Angewandte Chemie, Vol. 86 (9), page 349 (1974) , and the methods of the references cited therein. Commercially available products are also applicable. The addition amount of the compound of the formula (I) is preferably 10 ^-3 to 10 mol, more preferably 10-2 to 1 mol per mol of Ag. The compound of the formula (I) may be used singly or in combinations of two or more.

The compound of the formula (I) may be added to any layer which is on the same side of the support as the layer containing a silver salt of an organic acid, for example, a Sil an organic acid-containing layer, for example, to a silver organic acid-containing layer (an image-recording layer), a photosensitive layer, an intermediate layer, and a protective layer, and is preferably added to an intermediate layer or a protective layer.

The invention Compound of formula (I) may be added in any form be, e.g. as a solution, a powder or dispersion of solid fine granules. A dispersion of solid Fine particles are prepared using well known Atomizing agent, e.g. a ball mill, a vibrating ball mill, a Sand mill, a colloid mill, a jet mill, a roller mill etc. For the Dispersion of fine solid particles can be dispersing aids be used.

One inventive Photothermographic photosensitive material preferably comprises a photosensitive layer containing a photosensitive silver halide (a catalytically effective amount of a photocatalyst) and a photo-insensitive layer comprises. The photosensitive layer contains preferably a binder (generally a synthetic polymer) and an inventive scale-like silver salt of an organic acid. Further, the photosensitive contains Layer preferably a hydrazine compound (a super high contrast agent) and a tint adjusting means (to control the silver tint). The Photosensitive layer may include a plurality of layers. For example, the photothermographic photosensitive material in view of the gradation adjustment with a high-speed photosensitive layer and a photosensitive low-speed layer. The Order of arrangement of the high-speed photosensitive layer and the photosensitive low-speed layer is so, that the photosensitive low-speed layer on the bottom (closer on the carrier) or that the photosensitive high-speed layer on the Bottom can be arranged.

In addition to a dye-containing layer, i. a filter layer, and an antihalation layer may be the photosensitive layer with another functional layer, such as one Surface protective layer equipped be.

When carrier for the invention Photothermographic photosensitive material may be paper, polyethylene coated Paper, polypropylene-coated paper, parchment, fabric, a Sheet or a thin foil of a metal (e.g., aluminum, copper, magnesium, zinc), glass and with a metal (e.g., a chromium alloy, steel, silver, Gold, platinum) coated glass or plastic sheeting become. Preferably, transparent plastic films are used as the carrier, and examples of preferred plastics include polyalkyl methacrylate (e.g., polymethylmethacrylate), Polyester (e.g., polyethylene terephthalate (PET)), polyvinyl acetal, Polyamide (e.g., nylon) and cellulose esters (e.g., cellulose nitrate, Cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate) one. The carrier preferably has a thickness of 0-190 microns, more preferably 150-185 microns.

Of the carrier can be covered with a polymer. Examples of usable polymers include Polyvinylidene chloride, acrylic acid polymers (e.g., polyacrylonitrile, methyl acrylate), polymers of unsaturated dicarboxylic acids (e.g., itaconic acid, Acrylic acid), Carboxymethyl cellulose and polyacrylamide. Copolymers can also be used. Instead of covering with a polymer can provided a primer layer containing a polymer become.

The inventively used silver halide is not particularly limited, and inventively can be any, selected of silver bromide, silver iodide, silver chloride, silver chlorobromide, Silver iodobromide and silver chloroiodobromide. The Distribution of the halogen composition in the grain may be uniform or the halogen composition may be gradual or continuous mutable be. Preferably, silver halide grains having a core / shell structure used. Grain structures with a double structure to quadruple structure are preferred. Core / shell grains having a double structure to quadruple structure are more preferable usable. Techniques for the Localization of Silver Bromide on the surface of silver chloride or silver chlorobromide grains may be preferably used.

The grain size of the silver halide grain 0.001-0.04 μm, preferably 0.005-0.04 μm. The projected with an electron microscope from 10 projected areas of grains received circle equivalents Diameters are averaged and according to the invention as the grain diameter of Silver halide grain accepted.

The addition amount of the silver halide is preferably 0.03-0.6 g / m ² , more preferably 0.05-0.4 g / m ^2, and most preferably 0.1-0.4 g / m ² , as a coated amount per m ^{2 of} the photothermographic material.

The inventively Usable photosensitive silver halide can be applied using of methods well known in the industry For example, the methods can be used in Research Disclosure, Item 17929 (June, 1978) and U.S. PS 3,700,458 are disclosed. More specifically, the silver halide is prepared as a silver halide emulsion by reaction of silver nitrate with a soluble Halide. Silver halide can be prepared by reaction a silver soap with a halogen ion and conversion of the soap content the silver soap in halogen. Alternatively, a halogen ion while of the silver soap generation step.

silver is generally spectrally sensitized before use.

spectral are disclosed in JP-A-60-140335, JP-A-63-159841, JP-A-63-231437, JP-A-63-259651, JP-A-63-304242, JP-A-63-15245 and US-PSen 4 639 414, 4 740 455, 4 741 966, 4 751 175 and 4 835 096.

The Photosensitive layer and the photosensitive layer included preferably a binder. In general, as a binder a colorless and transparent or translucent polymer used.

Of the invention Effect is increased when the photosensitive layer is prepared by coating a coating solution, in the 30% by weight or more of the solvent be formed by water, and then drying, and further by using a polymer latex which is in an aqueous Solvent system (Water solvent) soluble or dispersible, in particular with an equilibrium moisture content from 25 ° C and 60% relative humidity of 2% by weight or less as the main binder the photosensitive layer (70% by weight or more, preferably 80% by weight or more of the total binder of the photosensitive Layer). The invention most preferred polymer is a polymer so prepared is that the ionic conductivity 2.5 mS / cm or less. Such a polymer can be prepared by a process in which the polymer produced under a cleaning treatment Use of a film is subjected to separation function.

An "aqueous solvent system" in which the major binder (hereinafter referred to as "inventive polymer") of invention photosensitive layer soluble or dispersible, as used herein, is water or water in mixture with a water-miscible organic solvent in a concentration of 70% by weight or less. As water-miscible organic solvents are illustrative alcohols, such as methyl alcohol, ethyl alcohol, Propyl alcohol, cellosolve such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide.

The System of a so-called dispersing state, wherein a polymer thermodynamically unresolved is, according to the invention also as aqueous Solvent system designated.

An "equilibrium moisture content at 25 ° C and 60% relative humidity" as used in the present invention can be represented as follows, wherein the weight of the polymer under equilibrium moisture conditions at 25C and 60% relative humidity W1 and the weight of the polymer at 25 ° C in the dry state Where is: Equilibrium moisture content at 25 ° C and 60% relative humidity = [(W1-W0) / (W0) x 100 (wt%)

Regarding the Definition and method of measurement of moisture content For example, on Polymer Engineering, Lecture 14, "Test Method of Polymeric Materials ", compiled by Kobunshi-Gakkai, published directed by Chijin Shokan Co., Ltd.

Of the Equilibrium moisture content at 25 ° C and 60% relative humidity of the inventive Polymers is preferably 2% by weight or less, more preferably 0.01-1.5% by weight, and more preferably 0.02-1 wt%.

The polymers of the present invention are not particularly limited as long as they are soluble or dispersible in the aqueous solvent system described above and have an equilibrium wetness content content at 25 ° C and 60% relative humidity of 2 wt.% or less. Among these polymers, polymers which are dispersible in an aqueous solvent system are particularly preferred.

Examples for dispersion conditions are latexes in which fine particles of solid polymers are dispersed, and dispersions in which polymer molecules in the molecular state or are dispersed to form micelles, and among these may be any preferably used.

hydrophobic Polymers, such as an acrylic resin, a polyester resin Gum-based resin (e.g., an SBR resin), a polyurethane resin, a vinyl chloride resin, a vinyl acetate resin, a vinylidene chloride resin and a polyolefin resin can preferably used. The polymers can be unbranched, branched or crosslinked polymers. As polymers, any selected from Homopolymers in which individual monomers are polymerized, and Copolymers in which two or more monomers are copolymerized, be used. When copolymers are used, any, selected from random copolymers and block copolymers. The Molecular weight of the polymers is 5,000-1,000,000, preferably 10,000-200,000, based on the number average molecular weight. If the molecular weight is too low is the mechanical strength the emulsion layer insufficient, whereas if it is too large is, the film-forming properties are adversely deteriorated.

The invention Polymers include the aforementioned polymers dispersed in one aqueous Dispersion medium system. "Aqueous Dispersion medium system " as used herein means a dispersion medium wherein 30 wt.% Or more of the composition is formed by water. As dispersion states can any, selected us an emulsified dispersion, a micelle dispersion and a Dispersion in which polymers with hydrophilic regions in the molecule in molecular State are dispersed, but will be special preferably uses latexes.

P-1:

Latex, das MMA (7=)-EA (27)-MAA (3) umfasst (Molekulargewicht: 37.000)

P-2:

Latex, das MMA (70) -2EHA (20) -St (5-AA (5) umfasst (Molekulargewicht: 40.000)

P-3:

Latex, das St (50) -Bu (47) -MAA (3) umfasst (Molekulargewicht: 45.000)

P-4:

Latex, das St (69) -Bu (29) -AA (3) umfasst (Molekulargewicht: 60.000)

P-5:

Latex, das St (70) -Bu (27) -IA (3) umfasst (Molekulargewicht: 120.000)

P-6:

Latex, das St (75)-Bu (24)-AA (1) umfasst (Molekulargewicht: 108.000)

P-7:

Latex, das St (60) -Bu (35-DVB (3) -MAA (2) umfasst (Molekulargewicht: 150.000)

P-8:

Latex, das St (70)-Bu (25)-DVB (2)-AA (3) umfasst (Molekulargewicht: 280.000)

P-9:

Latex, das VC (50) -MMA (20) -EA (20) -AN (5) -AA (5) umfasst (Molekulargewicht: 80.000)

P-10:

Latex, das VDC (85) -MMA (5) -EA (5) -MAA (5) umfasst (Molekulargewicht: 67.000)

P-11:

Latex, das Et 90)-MAA (10) umfasst (Molekulargewicht: 12.000)

P-12:

Latex, das St (70) -2EHA (27) -AA (3) umfasst (Molekulargewicht: 130.000)

P-13:

Latex, das MMA (63)-EA (35)-AA (2) umfasst (Molekulargewicht: 33.000)

Specific examples of preferred polymers are shown below. Hereinafter, the polymers based on the raw material monomers will be referred to, the numerical values in parentheses are wt%, and the molecular weights are the number average molecular weights.

P-1:

Latex comprising MMA (7 =) - EA (27) -MAA (3) (molecular weight: 37,000)

P-2:

Latex comprising MMA (70) -2EHA (20) -St (5-AA (5) (molecular weight: 40,000)

P-3:

Latex comprising St (50) -Bu (47) -MAA (3) (molecular weight: 45,000)

P-4:

Latex comprising St (69) -Bu (29) -AA (3) (molecular weight: 60,000)

P-5:

Latex comprising St (70) -Bu (27) -IA (3) (molecular weight: 120,000)

P-6:

Latex comprising St (75) -Bu (24) -AA (1) (molecular weight: 108,000)

P-7:

Latex comprising St (60) -Bu (35-DVB (3) -MAA (2) (molecular weight: 150,000)

P-8:

Latex comprising St (70) -Bu (25) -DVB (2) -AA (3) (molecular weight: 280,000)

P-9:

Latex comprising VC (50) -MMA (20) -EA (20) -AN (5) -AA (5) (molecular weight: 80,000)

P-10:

Latex comprising VDC (85) -MMA (5) -EA (5) -MAA (5) (molecular weight: 67,000)

P-11:

Latex comprising Et 90) -MAA (10) (molecular weight: 12,000)

P-12:

Latex comprising St (70) -2EHA (27) -AA (3) (molecular weight: 130,000)

P-13:

Latex comprising MMA (63) -EA (35) -AA (2) (molecular weight: 33,000)

The above abbreviations stand for the following monomers. MMA: methyl methacrylate, EA: ethyl acrylate, MAA: methacrylic acid, 2EHA: 2-ethylhexyl acrylate, St: styrene, Bu: butadiene, AA: acrylic acid, DVB: Divinylbenzene, VC: vinyl chloride, AN: acrylonitrile, VDC: vinylidene chloride, Et: ethylene and IA: itaconic acid.

The The polymers described above are commercially available and the following polymers are used. Examples of acrylic resins are Sebian A-4635, 46583 and 4601 (manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811, 814, 821, 820 and 857 (manufactured by Nippon Zeon Co., Ltd.), examples of Polyester resins are FINETEX ES650, 611, 675 and 850 (manufactured from Dainippon Chemicals and Ink Co., Ltd.), WD size and WMS (manufactured from Eastman Chemical Co.), examples of polyurethane resins are HYDRAN AP10, 20, 30 and 40 (manufactured by Dainippon Chemicals and Ink Co., Ltd.), examples of Rubber-based resins are LACSTAR 7310K, 3307B, 4700H and 7132C (manufactured by Dainippon Chemicals and Ink Co., Ltd.), Nipol Lx416, 410, 438C and 2507 (manufactured by Nippon Zeon Co., Ltd.), examples for vinyl chloride resins are G351 and G576 (manufactured by Nippon Zeon Co., Ltd.), examples for vinylidene chloride resins L502 and L513 (manufactured by Asahi Chemical Industry Co., Ltd.) and examples of Olefin resins are Chemipearl S120 and SA100 (manufactured by Mitsui Petrochemical Industries, Ltd.).

These Polymers can can be used individually as polymer latices, or if necessary, two or more more polymers are mixed together.

According to the invention especially preferred are styrene-butadiene copolymer latexes used. The weight ratio the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene copolymers is preferably 40/60 to 95/5. The through the styrene monomer unit and the butadiene monomer unit in the copolymer occupied portion is preferably 60-99% by weight. The preferred molecular weight is that Same as above.

According to the invention preferred used styrene-butadiene copolymer latexes are the aforementioned P-3 and P-8 and the commercially available Products LACSTAR-3307B, 7132C and Nipol Lx416.

To the photosensitive layer of the photosensitive material of the present invention can hydrophilic polymers such as gelatin, polyvinyl alcohol, Methylcellulose and hydroxypropylcellulose. The Addition amount of these hydrophilic polymers is preferably 30% by weight or less, more preferably 20% by weight or less, based on the total amount of the binder in the photosensitive layer.

The invention Photosensitive layer is preferably formed from polymer latices. The weight ratio of total binder / organic silver salt in the photosensitive Layer is preferably 1/10 -10 / 1, more preferably 1 / 5-4 / 1.

The weight ratio Total binder / silver halide is preferably 400/5, preferably 200/10.

The total amount of the binder in the photosensitive layer of the present invention is preferably 0.2-30 g / m ² , more preferably 1-15 g / m ² . The photosensitive layer of the present invention may contain a crosslinking agent for crosslinking and a surfactant for improving coating properties.

The solvent for the coating solution for the Photosensitive layer of the photosensitive material of the present invention (Solvent and dispersion medium are abbreviated together as a solvent is an aqueous one Solvent system containing 30% by weight or more of water. As other components as water can in the coating solution water-miscible organic solvents can be used in any desired manner, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, Methyl cellosolve, ethyl cellosolve, dimethylformamide and ethyl acetate. The water content in the solvent for the coating solution is preferably 50% by weight or more, more preferably 70% by weight or more. Preferred examples of the compositions of the solvent close additionally water / methyl alcohol = 90/10 (wt.%), water / methyl alcohol = 70/30, water / methyl alcohol / dimethylformamide = 80/15/5, water / methyl alcohol / ethyl cellosolve = 85/10/5, water / methyl alcohol / isopropyl alcohol = 85/10/5, etc. one.

It is for the photosensitive layer or the photosensitive layer preferably that it further contains a super high contrast agent. If the photothermographic (photosensitive) material in the range of Photography for The pressure used is the reproduction of a continuous one Gradation image by dots and a line image of importance. The reproduction of a dot picture and a line picture can be done by Use of a super high-contrast enhancing agent can be improved. As super high-contrast-increasing Means can Hydrazine compounds, quaternary Ammonium compounds or acrylonitrile compounds (e.g., as in U.S. Pat 5,545,515). Particularly preferred Hydrazine compounds used.

Hydrazine compounds include a compound wherein hydrazine (H ₂ N-NH ₂ ) and at least one of the hydrogen atoms are substituted. As the substituent, an aliphatic, aromatic or heterocyclic group is bonded directly to the nitrogen atom of the hydrazine, or an aliphatic, aromatic or heterocyclic group is bonded to the nitrogen atom of the hydrazine via a linking group. Examples of linking groups include -CO-, -CS-, -SO ₂ -, -POR- (P is an aliphatic, aromatic or heterocyclic group), -CNH- and combinations thereof.

Hydrazine compounds are disclosed in U.S. Patent Nos. 5,474,738, 5,496,695, 5,512,411, 5,536,622, JP-B-6-77138 (the term "JP-B" as used herein means a "tested Japanese patent patent Publication "), JP-B-6-93082, JP-A-6-230497, JP-A-6-289520, JP-A-6-313951, JP-A-7-5610, JP-A-7 77783 and JP-A-7-104426.

The Hydrazine compound may be in a suitable organic solvent disbanded and then to the coating solution for the Photosensitive layer may be added. Examples of organic solvent include alcohols (e.g., methanol, ethanol, propanol, fluorinated Alcohol), ketones (e.g., acetone, methyl ethyl ketone), dimethylformamide, Dimethyl sulfoxide and methyl cellosolve. The hydrazine compound can in an oily (Additional) solvent disbanded be, and the solution can in the coating solution be emulsified. Examples of oily (additional) solvent close Dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, Diethyl phthalate, ethyl acetate and cyclohexanone. Furthermore, a solid dispersion of a hydrazine compound is added to the coating solution. The dispersion of the hydrazine compound can be carried out using well-known dispersing devices, such as for example, a ball mill, a colloid mill, a Mantin Gaulin, a microfluidizer or an ultrasonic disperser.

The addition amount of the super high contrast agent is preferably 1 × 10 ^-6 to 1 × 10 ^-2 mol, more preferably 1 × 10 ^-5 to 5 × 10 ^-3 mol, and most preferably 2 × 10 ^-5 to 5 × 10 ^-3 mol per mole of silver halide.

In addition to a super high contrast increasing Agent can use a high-contrast accelerator according to the invention become. examples for High contrast accelerating agents close an amine compound (e.g., as disclosed in U.S. Patent No. 5,545,506), a hydroxamic acid (e.g. as disclosed in U.S. Patent No. 5,545,507), acrylonitriles (e.g., as in U.S. Pat 5,545,507) and a hydrazine compound (e.g., as in US Pat 558 983).

It It is preferred that a photosensitive layer or photosensitive Layer a Tönungseinstellmittel (a sounder) contains. A tint adjusting agent is described in Research Disclosure No. 17029.

Examples for tint control include imides (e.g., phthalimide); cyclic imides (e.g., succinimide); Pyrazoline-5-one (e.g., 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole); Quinazolinone (e.g. Quinazolinone, 2,4-thiazolidondione); Naphthalimides (e.g., N-hydroxy-1,8-naphthalimide); Cobalt complexes (e.g., cobalt hexamine trifluoroacetate); Mercaptans (e.g. 3-mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboxyimides (e.g. N-dimethylaminomethyl) phthalimide), blocked pyrazoles (e.g., N, N'-hexamethylene-1-carbamoyl-3,5-dimethylpyrazole); combinations Isothiuronium derivatives (e.g., 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) with photo-bleaches (e.g., 2-tribromomethylsulfonyl) benzothiaazole); merocyanine (e.g., 3-ethyl-5 - [(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione); Phthalazinone compounds and metal salts thereof (e.g., phthalazinone, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphtalazinone, 2,3-dihydro-1,4-phthalazinedione, 8-Methylphthalazin); Combinations of phthalazinone compounds and sulfinic acid derivatives (e.g., sodium benzenesulfinate); Combinations of phthalazinone compounds and sulfonic acid derivatives (e.g., sodium p-toluenesulfonate); Phthalazine and derivatives thereof (e.g., phthalazine, 6-isopropylphthalazine, 6-methylphtalazine); Combinations of phthalazines and phthalic acids; combinations from phthalazines or phthalazine adducts with dicarboxylic acids (e.g. preferably o-phenylenic acid) or anhydrides thereof (e.g., maleic anhydride, phthalic acid, 2,3-naphthalenedicarboxylic acid, phthalic anhydride, 4-methylphthalic acid, 4-nitrophthalic acid, Tetrachlorophthalic anhydride); quinazolinediones; benzoxazine; Naphthooxazinderivate; Benzoxazine-2,4-dione; Pyrimidines, asymmetric triazines (e.g., 2,4-dihydroxypyrimidine); Tetraazapentaline derivatives (e.g., 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentals) one. Among these compounds, phthalazines are particularly preferred.

The Tönungseinstellmittel are preferably in the surface the photosensitive layer in an amount of 0.1-50 mol%, further preferably 0.5-20 mol%, per mole of silver.

To a photosensitive layer or a photosensitive layer (Preferably, a photosensitive layer), an anti-fogging agent be added. As anti-fogging agent according to the invention rather mercury-free compounds (e.g., those as in U.S. Patents 3) 874 946, 4 546 075, 4 452 885, 4 756 999, 5 028 523, the British Patent Applications Nos. 92 221 338.4. 9,300,147.7, 9,311,790.1 and JP-A-59-57234) as mercury compounds (as in US Pat 3,589,903).

Especially preferred anti-foggants are heterocyclic compounds with a halogen (e.g., F, Cl, Br, I) -substituted methyl group.

It is preferred to use polyvinyl alcohol (PVA) in the photothermographic material, especially the Protective layer of the photothermographic (photosensitive) material according to the present invention to use. Examples of the PVA usable in the present invention are shown below.

Examples for completely hydrolyzed Products:

• PVA-105 [polyvinyl alcohol (PVA) content: 94.0% by weight or more, degree of saponification: 98.5 ± 0.5 mol% Sodium acetate content: 1.5% by weight or less, content on fleeting Ingredients: 5.0% by weight or less, Viscosity (4 wt. %, 20 ° C) : 5, 6 ± 0, 4 CPS]
• PVA-110 [PVA content: 94.0% by weight, degree of saponification: 98.5 ± 0.5 mol%, Sodium acetate content: 1.5% by weight. Volatile content: 5, .0 % By weight, viscosity (4 Weight%, 20 ° C): 11.0 ± 0.8 CPS]
• PVA-117 [PVA content: 94.0% by weight, degree of saponification: 98.5 ± 0.5 mol%, Sodium acetate content: 1.0% by weight. Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 28, 0 ± 3, 0 CPS]
• PVA-117H [PVA content: 93.5% by weight, degree of saponification: 99.6 ± 0.3 mol%, Sodium acetate content: 1.85% by weight, volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 29, 0 ± 3, 0 CPS]
• PVA-120 [PVA content: 94.0% by weight, degree of saponification: 98.5 ± 0.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 39, 5 ± 4, 5 CPS]
• PVA-124 [PVA content: 94.0% by weight, degree of saponification: 98.5 ± 0.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 60.0 ± 6.0 CPS]
• PVA-124H [PVA content: 93.5% by weight, degree of saponification: 99.6 ± 0.3 mol%, sodium acetate content: 1.85% by weight. Content of volatile Ingredients: 5.0% by weight, Viscosity (4% by weight, 20 ° C): 61, 0 ± 6, 0 CPS]
• PVA-CS [PVA content: 94.0% by weight, degree of saponification: 97.5 ± 6.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 27, 5 ± 3, 0 CPS]
• PVA-CST [PVA content: 94.0% by weight, degree of saponification; 96.0 ± 0.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 27.0 ± 3.0 CPS]
• PVA-HC [PVA content: 90.0% by weight, degree of saponification: 99.85 mol% or more, sodium acetate content: 2.5% by weight, volatile content Ingredients: 8.5% by weight, Viscosity (4% by weight, 20 ° C): 25.0 ± 3.5 CPS] etc. (All the above products are manufactured by Kuraray Co., Ltd.)

Examples of partial saponified products:

• PVA-203 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 Wt.%. Viscosity (4 Weight%, 20 ° C): 3.4 ± 0.2 CPS]
• PVA-204 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 3.9 ± 0.3 CPS]
• PVA-205 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 5.0 ± 0.4 CPS]
• PVA-210 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.0 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 9, 0 ± 1, 0 CPS]
• PVA-217 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.0 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 22, 5 ± 2, 0 CPS]
• PVA-220 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.0 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 30.0 ± 3.0 CPS]
• PVA-224 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 44, 0 ± 4, 0 CPS]
• PVA-228 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 65, 0 ± 5, 0 CPS]
• PVA-235 [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 95, 0 ± 15, 0 CPS]
• PVA-217EE [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.0 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 23, 0 ± 3, 0 CPS]
• PVA-217E [PVA content: 94.0% by weight, saponification degree; 88.0 ± 1.0 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 23.0 ± 3.0 CPS]
• PVA-220E [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.0 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 31.0 ± 4.0 CPS]
• PVA-224E [PVA content: 94.0% by weight, degree of saponification: 88.0 ± 1.0 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 45, 0 ± 5, 0 CPS]
• PVA-403 [PVA content: 94.0% by weight, degree of saponification: 80.0 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 3.1 ± 0.3 CPS]
• PVA-405 [PVA content: 94.0% by weight, degree of saponification: 81.5 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C) : 4, 8 ± 0, 4 CPS]
• PVA-420 [PVA content: 94.0% by weight, degree of saponification: 79.5 ± 1.5 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % Wt.]
• PVA-613 [PVA content: 94.0% by weight, degree of saponification: 93.5 ± 1.0 mol%, Sodium acetate content: 1.0% by weight, Volatile content: 5.0 % By weight, viscosity (4 Weight%, 20 ° C): 16.5 ± 2.0 CPS]
• L-8 [PVA content: 96.0% by weight, degree of saponification: 71.0 ± 1.5 mol%, Sodium acetate content: 1.0% by weight (ash content), volatile content Ingredients: 3.0% by weight, Viscosity (4% by weight, 20 ° C): 5.4 ± 0.4 CPS] etc. (All the above products are manufactured by Kuraray Co., Ltd. produced).

The above measured values are according to JIS K-6726-1977.

According to the invention modified Polyvinyl alcohols are used, as described in Koichi Naganp et al., Poval, published from Kobunshi-kankoKai. It can be used those those having a cation, an anion, an -SH compound, an alkylthio compound and a silanyl compound.

Examples of modified polyvinyl alcohol (modified PVA) are as follows:
as C-polymer: C-118, C-318, C-318-2A and C-506 (manufactured by Kuraray Co., Ltd.)
as HL polymer: HL-12E, HL-1203 (manufactured by Kuraray Co., Ltd.)
as HM polymer: HM-03 and HM-N-03 (manufactured by Kuraray Co., Ltd.)
as K polymer: KL-118, KL-318, KL-506, KM-118T and KM-618 (manufactured by Kuraray Co., Ltd.)
as M polymer: M-115 (manufactured by Kuraray Co., Ltd.)
as MP polymer: MP-102, MP-202 and MP-203 (manufactured by Kuraray Co., Ltd.)
as R-polymer: R-1130, R-2105 and R-2130 (manufactured by Kuraray Co., Ltd.)
as V polymer: V-2250 (manufactured by Kuraray Co., Ltd.)

The coating amount of the polyvinyl alcohol of the protective layer (per layer) is preferably 0.3-4.0 g / m ² , more preferably 0.3-2.0 g / m ² per m ^{2 of} carrier.

The invention photothermographic material, in particular the protective layer of the Photothermographic (photosensitive material) preferably contains a matting agent. Matting agents generally include fine particles of water-insoluble organic or inorganic compounds.

Optional matting agents can be used in the invention. Organic matting agents as disclosed in U.S. Patents 1,939,213, 2,701,245, 2,322,037, 3,262,782, 3,539,344 and 3,767,448 and inorganic matting agents as disclosed in US Pat. Nos. 1,260,772, 2,192,241, 3,257,206, 3,370,951, 3,523,022 and 3,769,020 are well known in the art and may be used in the present invention become. As specific examples of organic compounds which can be used as matting agents, examples of water-dispersible vinyl polymers include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymers, polystyrene, styrene-divinylbenzene copolymers, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc. Examples of cellulose derivatives include methyl cellulose, cellulose acetate, cellulose acetate propionate, etc. Examples of starch derivatives include carboxyl starch, carboxynitrophenyl starch, urea-formaldehyde starch reaction products, etc., hardened gelatin treated with well-known curing agents, and hardened gelatin as microencapsulated hollow particles by coacervation hardening and can preferably be used. As examples of inorganic compounds, there may be preferably used silica, titania, magnesia, alumina, barium sulfate, calcium carbonate, silver chloride and silver bromide desensitized by a publicly known method, glass and diatomaceous earth. These matting agents can be mixed with various types of substances as needed.

According to the invention, preferably Matting agent used with a particle size of 2-6 microns become. The particle size distribution of the matting agent may be wide or narrow. Da matting agent the cloudiness of the photosensitive material and surface gloss, on the other hand, is it desirable the particle size, the particle shape and particle size distribution in manufacturing matting agents or mixing several matting agents to adjust to the required conditions.

The circle-equivalent Diameter, which consists of the projected areas of the particles by means of a Electron microscopes are averaged, and this Value is according to the invention assumed as the particle diameter of the matting agent.

The coating amount of the matting agent is 1-400 mg / m ² , more preferably 5-300 mg / m ² , and it is particularly preferable that the coating amount of the matting agent having a particle size of 4 μm or more is 5-150 mg / m ² ,

If a matting agent in the layer on the surface side an image-recording layer or a photosensitive layer is included, the protective layer is optimal. A protective layer may include two layers if required. When choosing the layers, the one additive, a film pH adjuster, an agent for adjusting the electrostatic charge, a UV absorber, a lubricant and a surfactant that are involved in the development participate, it is possible make the design so that the coating properties and suitability for manufacturing are consistent with the image quality. It is preferred that the outermost Protective layer together with a matting agent a surfactant Contains fluorine base.

Examples for surfactants fluorine-based are fluorine-based high molecular weight surfactants, as disclosed in JP-A-62-170950 and US Pat. No. 5,380,644, and surfactants fluorine-based as disclosed in JP-A-60-244945 and JP-A-63-188135.

It is according to the invention preferred, that in the outermost Protective layer containing a matting agent,

In a backing layer For example, a matting agent may be included, and in this case the layer containing the matting agent, preferably not the outermost one Layer on the back surface.

In any layer, selected from an image-recording layer (preferably a photosensitive Layer), a protective layer and a backside layer may be a curing agent be used. examples for hardener are in T.H. James, The Theory of the Photographic Process, 4th Edition, Pages 77-87, Macmillan Publishing Co., Inc. (1977), and polyvalent ones Metal ions as described on page 78 of the above reference, Polyisocyanates as disclosed in U.S. Patent 4,281,060 and JP-A-6-208193, Epoxy compounds as disclosed in U.S. Patent 4,791,042 and vinyl sulfone compounds, as disclosed in JP-A-62-89048, are preferred in the present invention used.

As the surface protective layer of the present invention, an adhesion preventing material can be used. Examples of adhesion-preventing materials include waxes, silica particles, styrene-containing elastomeric block copolymers (eg, styrene-butadiene-styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate, and mixtures thereof. Furthermore, the inventive Ober surface protection layer containing a crosslinking agent for crosslinking and a surfactant for improving the coating properties.

The Image-recording layer or the protective layer of the image-recording layer of the invention may contain light-absorbing substances or filter dyes, as in U.S. Patents 3,253,921, 2,274,782, 2,527,583 and 2,956,879 disclosed. Furthermore, can Dyes are incorporated as disclosed in U.S. Patent 3,282,699.

The Image-recording layer or the protective layer of the image-recording layer of the invention may contain a matting agent, e.g. Starch, titanium dioxide, zinc oxide, Containing silica or polymer beads beads as disclosed in U.S. Patents 2,992,101 and 2,701,245. The degree of matting the emulsion surface is not particularly limited as long as white spots unevenness does not occur, however, is the Beck smoothness preferably 200-10,000 seconds, more preferably 300-10,000 Seconds.

The invention Photothermographic (photosensitive) material is preferred a single-sheet type material (a type used to produce a Image on the photothermographic (photosensitive) material without using another sheet, e.g. a picture-taking Material that is capable of).

The invention Photothermographic (photosensitive) material may further include Surfactant, an antioxidant, a stabilizer, a plasticizer, a UV absorber or a coating aid. Various Additives become either a photosensitive layer or a photosensitive layer. Regarding the Add these additives to WO 98/36322, EP-A-803764, JP-A-10-186567 and JP-A-10-18568.

The invention Photosensitive layer can be used as a plasticizer and as a lubricant polyhydric alcohols (e.g., glycerols and diols, as disclosed in U.S. Patent No. 2,960 404), fatty acids or fatty acid esters, such as in U.S. Patents 2,588,765 and 3,121,060, and silicone resins, as disclosed in GB-PS 955 061.

It it is preferred that the photosensitive layer in the photothermographic according to the invention (Photosensitive) material containing a decolorizing dye and a base precursor, whereby the function as a filter layer or halo-protective layer produced becomes. A photothermographic (photosensitive) material usually has additionally to photosensitive layer photosensitive layers. Photo insensitive Layers can with reference to the arrangement in (1) a protective layer on a photosensitive Layer (further from the carrier removed), (2) an intermediate layer sandwiched between Plurality of photosensitive layers or between a photosensitive layer Layer and a protective layer is provided, (3) a primer layer, provided between a photosensitive layer and a support and (4) a backside layer, provided on the opposite side of the photosensitive layer is to be divided. A filter layer is transformed into a photosensitive material provided as a layer (1) or (2). An atrial protective layer will in a photosensitive material as a layer (3) or (4) provided.

To One and the same photosensitive layer are preferably a decolorizing Dye and a base precursor added. You can separated from each other to two adjacent photo-insensitive layers be added. Furthermore, a barrier layer between two photo-insensitive layers are provided. According to the invention "closes a layer, the a decolorizing Dye and a base precursor contains "the case, in a plurality of layers adjacent to each other a decolorizing one Dye and a base precursor separated from each other.

To the coating solution of a photosensitive layer, a decolorizing dye as a solution, an emulsion, a fine particulate solid dispersion or a polymer-impregnated product may be added. Further, to a photosensitive layer, a dye may be added using a polymer stain. These addition methods are the same as the methods used to add dye to general photothermographic (photosensitive) materials. Latexes used in polymer-impregnated products are described in US Patent 4,199,363, DE-PS Nos. 2,541,274 and 2,541,230, EP 029 104 and JP-B-53-41091. With respect to the emulsification process for adding a dye to a solution containing a dissolved polymer, there is a disclosure in 88/00723.

The addition amount of the decoloring dye is determined based on the purpose of the dye. In general, a decolorizing dye is used in an amount having an optical density (Absor banz) which exceeds 0.1 when measured at a desired wavelength. The optical density is preferably 0.2-2. The addition amount of a dye for obtaining such an optical density is generally about 0.001 to about 1 g / m ^2, preferably about 0.005 to about 0.8 g / m ² and most preferably about 0.01 to about 0.2 g / m ² .

The discoloration the inventive Dyestuffs result in a reduction in optical density to 0.1 or less. It can two or more types of decolorizing Dyes in combination with each other in a thermal recording material from decolorizing Type and a photothermographic (photosensitive) material be used. It can also two or more types of base precursor in combination with each other be used.

The invention Photosensitive material can be treated with an antistatic layer or an electrically conductive Equipped be, e.g. Layers that are soluble Salts (e.g., chloride, nitrate), metal deposition layers, layers, which contain ionic polymers as described in US Pat. Nos. 2,861,056 and 3,206,312, and insoluble inorganic Salts as disclosed in U.S. Patent 3,429,451.

The A process for obtaining a color image with the photothermographic according to the invention (Photosensitive) material is in JP-A-7 13295, page 10, left Column, line 43 to page 11, left column, line 40 discloses. Dye image stabilizers are disclosed in British Patent 1,326,889, the U.S. Patent Nos. 3,432,300, 3,698,919, 3,574,627, 3,573,050, 3,764,237, and U.S. Patent Nos. 4,342,347; 4 042 394.

The invention photothermographic material, especially photothermographic (photosensitive) Material, can be coated by any method. In particular, you can the extrusion coating, lubricious coating, curtain coating, Dip coating, blade coating, flow coating and various coating methods, including extrusion coating under Use of feed hoppers, as disclosed in U.S. Patent 2,681,294. The extrusion coating and lubricious coating, as in Stephen F. Kistler, Peter M. Schweizer, Liquid Film Coating, pages 399-536, Chapman & Hall Co. (1997) preferably applied, and particularly preferred is the lubricious coating applied. examples for the shapes of the slide coaters used in the slip coating are described in ibid., page 427, Figure 11b.1. There can be two or more layers simultaneously according to the procedures, as in ibid., Pages 399-536, U.S. Patent 2,761,791 and British Patent 837,095, if desired. Simultaneous coating methods are preferably used.

According to the invention, the Purpose of improving coating properties and electrical Charge surfactants are used. It can be in any selection any surfactants can be used, e.g. nonionic, anionic, cationic and fluorine-based surfactants. In particular, high molecular weight Fluorine-based surfactants as disclosed in JP-A-62-170950 and US Pat. No. 5,380,644 discloses fluorine-based surfactants, as in JP-A-60-244945 and JP-A-63-188135 discloses polysiloxane-based surfactants as in US-PS 3,885,965, and polyalkylene oxide and anionic surfactants, as disclosed in JP-A-6-301140 can be exemplified become.

In a photothermographic (photosensitive) material becomes Picture by heating generated after the image exposure. This heat builds up a black-tinted silver image generated. The image exposure is preferably performed with a laser. The heating temperature in the heat development is preferably 80-250 ° C, more preferably 100-200 ° C. The heating period is generally 1 second to 2 minutes. As a heat development process For example, a plate heating system is preferably used. The in JP-A-11-133572 and Japanese Patent Application 10-177610 disclosed plate heating systems are preferred, which represent methods in which uses a heat developing device , whereby a visible image is obtained by using a photothermographic (photosensitive) material in which a latent image was formed, at a heat development part is contacted with a heating medium. The aforementioned heating means includes a plate heater, and a plurality of pressure rollers is along a surface the plate heater opposite the plate heating arranged. The heat development is passed through the aforesaid photothermographic (photosensitive) material between the above pinch rollers and the plate heater.

As a heating method in the heat development method, there may be exemplified the embodiments described in U.S.P. 1 and 2 are shown.

A photothermographic (photosensitive) material transported to an image exposure area is raster-exposed with laser beams, etc., and subjected to heat development by means of transport rollers, etc. rich ( 18 ) after a latent image has been formed on the photothermographic (photosensitive) material. During transport, dusts on the back and front surfaces of the material are removed by a dust removal roller.

As in 1 shown is the heat development part ( 18 ) A part in which a latent image is converted to a visible image by heat development by heating the photothermographic (photosensitive) material. The present invention is characterized in that the heat generation part ( 18 ) a plate heater ( 120 ) and a plurality of pressure rollers ( 122 ), the plate heating ( 120 ) are arranged opposite one another.

The plate heater ( 120 ) is a plate-like heating element which encloses a heating unit such as nichrome wire deposited in a planar state, and which is held at the developing temperature of the photothermographic (photosensitive) material. The surface of the plate heater ( 120 ) is preferably coated with fluorine resins or stuck with a fluororesin sheet for the purpose of reducing the coefficient of friction or the given abrasion resistance.

The volatile content of the photothermographic (photosensitive) material is evaporated by heating during heat development, and as a result, the photothermographic photosensitive material is lifted from the heater (FIG. 120 ) and the contact of the photothermographic (photosensitive) material with the plate heater ( 120 ) occasionally becomes uneven. Therefore, it is also preferable to have concave and convex structures on the surface of the plate heater ( 120 ), whereby this steam is distributed.

Furthermore, it is preferable to generate a temperature gradient so that the temperature at both ends of the plate heater ( 120 ) is higher than the temperature in other areas, thereby compensating for the temperature reduction by heat distribution at both ends.

The pressure rollers ( 122 ) are at a predetermined distance in contact with a surface of the plate heater ( 120 ) at a distance which is less than the thickness of the photothermographic (photosensitive) material along the entire length of the transport direction of the plate heater ( 120 ), and these pressure rollers ( 122 ) and the plate heater ( 120 ) form the path of the photothermographic (photosensitive) material.

By making the distance of the path of the photothermographic (photosensitive) material smaller than the thickness of the photothermographic (photosensitive) material, the photothermographic (photosensitive) material can be prevented from being thrown up. Feed rollers ( 126 ) for supplying the photothermographic (photosensitive) material into the heat developing part ( 18 ) from the direction of the indicated arrow and outfeed rollers ( 128 ) for carrying out the photothermographic (photosensitive) material in the direction of the shown arrow after the heat development are arranged at both ends of the path of the photothermographic (photosensitive) material.

Furthermore, it is preferable to use a heat-insulating cover ( 125 ) for heat insulation on the surface side of the pressure rollers ( 122 ) on the plate heater ( 120 ) opposite side.

When the photothermographic (photosensitive) material is transported, the photothermographic (photosensitive) material stops for a moment when the tip of the photothermographic (photosensitive) material is pressed against the platen roller (Fig. 122 ) pushes. In this case, the same part of the photothermographic (photosensitive) material comes into contact with each pressure roller ( 122 ) when the pressure rollers ( 122 ) are arranged at the same distance, and the part of the photothermographic (photosensitive) material is for a long time against the plate heating ( 120 ), which occasionally results in the generation of a stripe-shaped uneven development extending in the width direction. Therefore, it is preferable that the distance of each pressure roller ( 122 ) adjust unevenly.

As in 2 shown, the structure of the heat development part ( 18 ) also be such that a drive roller ( 130 ) in contact with each pressure roller ( 122 ), wherein the development surface of each pressure roller ( 122 ) corresponds to the peripheral surface, and each pressure roller ( 122 ) is due to the rotation of the drive roller ( 130 ) turned.

In the above explanation, the plate heater ( 120 ) also comprise a plate component having a Includes heat conductor and a heat source, which are arranged on the side of the plate member on the heating side of the photothermographic (photosensitive) material opposite side.

If a photothermographic material is not a photosensitive silver halide contains is the heat development after a conventional Procedure performed.

The The present invention will be described in detail with reference to Examples explains however, the present invention should not be construed as being limited thereto.

EXAMPLE I-1

Preparation of a silver halide grain emulsion (1):

To 1.421 ml of distilled water were added 6.7 ml of a 1% by weight potassium bromide solution, 8.2 ml of 1N nitric acid and 21.8 g of phthalated gelatin. This mixed solution was stirred in a titanium-coated stainless reaction vessel while maintaining a temperature of 25 ° C. The solution (a1) (37.4 g of silver nitrate diluted to 159 ml with distilled water) and the solution (b1) (32.6 g of potassium bromide diluted to 200 ml with distilled water) were prepared. The total amount of the solution (a1) was added to the reaction vessel at a constant flow rate by a controlled double jet method while maintaining a pAg of 8.1 within 1 minute (solution (b1) was added by a controlled double jet method). Then, 30 ml of a 3.5 wt% aqueous hydrogen peroxide solution and further 33.6 ml of a 3 wt% aqueous benzimidazole solution were added. The solutions (a2) (solution (a1) was again diluted to 317.5 ml with distilled water) and (b2) (dipotassium hexachloroiridate was dissolved in solution (b1) so that the concentration was 1 × 10 ^-4 mol per mol Silver, and made up with distilled water to a final volume of 2 times solution (b1), ie 400 ml, diluted). The total amount of solution (a2) was added to the reaction vessel at a constant flow rate by a controlled double jet method while maintaining a pAg of 8.1 within 10 minutes (solution (b2) was added by a controlled double jet method). Then, 50 ml of a 0.5 wt% methanol solution of 2-mercapto-5-methylbenzimidazole was added, and further, the pAg was lowered to 7.5 with silver nitrate, and the pH was adjusted to 3.8 with 1 N sulfuric acid set and stop stirring. The reaction solution was subjected to precipitation, desalting and washing processes, then 3.5 g of deionized gelatin and then 1N sodium hydroxide were added to adjust the pH to 6.0 and the pAg to 8.2, thereby obtaining a Silver halide dispersion was obtained.

The grains in the thus prepared silver halide emulsion were pure silver bromide grains with an average sphere equivalent diameter of 0.031 μm and a sphere equivalent diameter variation coefficient of 11%. The grain size was the average of 1,000 grains, measured with an electron microscope. The (100) area ratio of these grains was 85% by the Kubelka-Munk method.

The temperature of the above emulsion was raised to 45 ° C with stirring and then 5 ml of a 0.5% by weight methanol solution of N, N'-dihydroxy-N ", N" -diethylmelamine and 5 ml of a 3 , 5 wt.% Methanol solution of phenoxyethanol, and 1 minute later, 3 × 10 ^-5 mol per mol of silver sodium benzenethiosulfonate. Another 2 minutes thereafter, a solid dispersion of the spectral sensitizing dye (1) (an aqueous gelatin solution) was added in an amount of 5 × 10 ^-3 mol per mol of silver, and another 2 minutes thereafter, 5 × 10 ^-5 mol per mol of silver of a tellurium compound added and the reaction solution matured for 50 minutes. Immediately before completion of the ripening, 2-mercapto-5-methylbenzimidazole in an amount of 1 x 10 ^-3 mol and mercapto compound (1) in an amount of 1.1 x 10 ^-3 mol, each per mol of silver, were added to the reaction solution , The temperature was lowered to 32 ° C. In this way, the silver halide grain emulsion (1) was prepared.

Preparation of silver halide grain emulsion (2):

Phthalated gelatin (22 g) and 30 mg of potassium bromide were dissolved in 700 ml of water, and the pH was adjusted to 5.0 at 35 ° C. An aqueous solution (159 ml) containing 18.6 g of silver nitrate and 0.9 g of ammonium nitrate and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 92/8 were immersed by a controlled double jet method within 10 minutes Maintaining a pAg of 7.7 added to the aforementioned solution. Subsequently, 476 ml of an aqueous solution containing 55.4 g of silver nitrate and 2 g of ammonium nitrate, and an aqueous solution, containing 1 x 10 ^-5 mol / l of dipotassium hexachloroiridate and 1 mol / l of potassium bromide, was added to the above solution by a controlled double jet method within 30 minutes while keeping the pAg at 7.7. Subsequently, 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added, the pH was lowered and the reaction solution subjected to coagulant precipitation and desalted. Then, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 8.2, thereby completing the production of silver iodobromide grains. The silver halide grains thus obtained were cubic grains having an iodine content in the core region of 8 mol% and an average of 2 mol%, an average grain size of 0.005 μm, a variation coefficient of the projected area diameter of 8% and a (100) area ratio of 88%. ,

The temperature of the silver halide grains thus obtained was raised to 60 ° C. To the above silver halide grains were added sodium thiosulfate (85 μmol), 1.1 x 10 ^-5 mol of 2,3,4,5,6-pentafluorophenylphosphine selenide, 1.5 x 10 ^-5 mol of a tellurium compound, 3.5 x 10 ^-8 mol Chloroauric acid and 2.7 x 10 ^-4 moles of thiocyanic acid, each per mole of silver, and then ripened for 120 minutes and then cooled to 40 ° C. Then, the spectral sensitizing dye (1) was added in an amount of 1 × 10 ^-4 mol and 2-mercapto-5-methylbenzimidazole in an amount of 5 × 10 ^-4 mol, and then the solution was cooled to 30 ° C, whereby the Silver halide grain emulsion (2) was obtained.

manufacturing of a scale-like fatty acid silver salt:

Behenic acid (87.6 g) (manufactured by Henkel Co., trade name Edenor C22-85R), 423 ml of distilled water, 49.2 ml of an aqueous solution containing 5 N NaOH, and 120 ml of t-butanol were mixed together and the mixture was for 1 hour at 75 ° C to give a sodium behenate solution. Separated from the sodium behenate solution were 206.2 ml of an aqueous Solution, containing 40.4 g of silver nitrate (pH 4.0) prepared and at Kept at 10 ° C. A reaction vessel, which contained 635 ml of distilled water and 30 ml of t-butanol at 30 ° C held, with the contents of the reaction vessel was stirred, the entire amount the above sodium behenate solution and the entire amount of the aqueous Silver nitrate solution were at constant flow rate within 62 minutes and 10 seconds or 60 minutes in such a way added to the reaction vessel, that only the watery Silver nitrate solution from The beginning of the addition was added to, 7 minutes and 20 seconds after the beginning of the addition of the aqueous Silver nitrate solution The addition of the sodium behenate solution was started and after completion the addition of the aqueous Silver nitrate solution was for For 9 minutes and 30 seconds, only the sodium behenate solution was added. The temperature in the reaction vessel was at 30 ° C kept and the outside temperature was controlled so that the temperature not increased. The tubes of the addition system of the sodium behenate solution were heated by a Dampfheizmantelverfahrens and the steam inlet opening was adjusted so that the solution temperature at the outlet of the tip of the pouring tip 75 ° C was. The piping system of the aqueous silver nitrate solution addition system was by circulation of cooling water in the outer Heated tube of the double tube. The positions at which the sodium behenate solution and the aqueous silver nitrate solution were added were in relation to the intervening ührach symmetrically arranged and the height the position was adjusted so that the reaction solution did not touched has been.

To Completion of the addition of the sodium behenate solution became the reaction solution the same temperature for Stirred for 20 minutes and then allowed to lower the temperature to 25 ° C. The solids content was then separated by suction filtration. The solids content was washed with water until the conductivity of the filtrate reached 30 μS / cm. In this way, a fatty acid silver salt was obtained. Of the The solid content obtained was not dried and used as a wet cake stored.

The Shape of the obtained silver behenate particles was measured by an electron microscope examined. The obtained silver behenate particles were scale-like Crystals with a = 0.14 μm, b = 0.4 μm and c = 0.6 μm im Average, and the coefficient of variation of the average Equivalent spherical diameter was 15%.

polyvinyl alcohol (Brand name: PVA-217) (7.4 g) and water became the wet cake in an amount corresponding to 100 g of dried solids, to a total of 385 g was added and then temporarily in a homomixer dispersed.

The preliminarily dispersed starting solution was dispersed three times using a disperser (trade name: Micro fluidizer M-110S-EH equipped with a G10Z interaction chamber manufactured by Micro Fluidex International Corp.). The pressure of the disperser was set at 1750 kg / cm ² . In this way, a silver behenate dispersion was obtained. The cooling operation was performed by installing Ren of heat exchange coils, each before and after the interaction chamber, and adjusting the desired dispersion temperature by adjusting the temperature of the cooling medium.

Preparation of acicular fatty acid silver salt (Comparison):

Under stir were 43.8 g of behenic acid (manufactured by Henkel Co., trade name: Edenor C22-85R), 730 ml distilled water and 60 ml of t-butanol of 79 ° C with 117 ml of an aqueous Solution, containing 1 N NaOH, over Staggered 55 minutes and the mixture was reacted for 240 minutes. Then were 112.5 ml of an aqueous Solution, containing 19.2 g of silver nitrate was added within 45 seconds and the solution was for Allowed to stand for 20 minutes, which lowered the temperature to 30 ° C. has been. The solids content was then separated by suction filtration. The solids content was washed with water until the conductivity of the filtrate 30 μS / cm reached. The solids content thus obtained was not dried and treated as a wet cake. Polyvinyl alcohol (brand name: PVA-205) (7.4 g) and water were added to the wet cake in an amount that 100 g of dried solids corresponded to a total amount of 385 g was added and then preliminarily dispersed in a homomixer.

The preliminarily dispersed starting solution was treated three times using a disperser (trade name: Microfluidizer M-110S-EH equipped with a G10Z interaction chamber manufactured by Micro Fluidex International Corp.). The pressure of the disperser was set at 1750 kg / cm ² . In this way, the silver behenate dispersion (B) was obtained. The silver behenate particles contained in the silver behenate dispersion thus obtained were acicular particles of a = 0.04 μm, b = 0.04 μm and c = 0.8 μm on average, and a coefficient of variation of 30%. The particle size was measured by Master Sizer X (manufactured by Malvern Instruments Ltd.). The cooling was performed by installing coil-shaped heat exchangers respectively before and after the interaction chamber, and adjusting the desired temperature of the dispersion by adjusting the temperature of the cooling medium.

Preparation of a 25 wt .-% - Reducing agent dispersion:

water (176 g) was added to 80 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 64 g of a 20% by weight aqueous solution solution of the modified polyvinyl alcohol Poval MP203 (manufactured by Kuraray Co., Ltd.) was added and thoroughly mixed to prepare a slurry. Zirconia beads (800 g) with an average diameter of 0.5 mm were in a vessel with the above slurry added and with a disperser (1/4 G sand mill, produced from Imex Co., Ltd.) for Dispersed for 5 hours, whereby the reducing agent dispersion obtained has been. The particles of the reducing agent dispersion thus obtained Reducing agent had an average particle diameter of 0.72 μm.

Preparation of a 10% by weight methanol solution the mercapto compound:

10 g of 3-mercapto-4-phenyl-5-heptyl-1,2,4-triazole were dissolved in 90 g of methanol dissolved.

Preparation of a 20% by weight Dispersion of a mercapto compound:

water (224 g) was added to 60 g of 3-mercapto-4-phenyl-5-heptyl-1,2,4-triazole and 32 g of a 20% strength by weight solution of the modified polyvinyl alcohol Poval MP203 (manufactured by Kuraray Co., Ltd.) was added and thoroughly mixed to prepare a slurry. Zirconia beads (800 g) with an average diameter of 0.5 mm were in a vessel with the above slurry and with a disperser (1/4 G sand mill, manufactured by Imex Co., Ltd.) for Dispersed for 10 hours, whereby the Mercaptoverbindungsdispersion was obtained. The particles of the mercapto compound dispersion thus obtained contained mercapto compound had an average particle diameter of 0.67 μm.

Preparation of a 30 wt .-% - Dispersion of an organic polyhalogen compound:

Water (224 g) was added to 44 g of tribromomethylphenylsulfone, 44 g of 3-tribromomethylsulfonyl-4-phenyl-5-tridecyl-1,2,4-triazole, 8 g of tribromomethyl-4- (2,4,6-trimethylphenylsulfonyl) phenyl sulfone, 0.8 g of sodium triisopropyl-α-naphthalenesulfonate and 48 g of a 20 wt% aqueous solution of the modified polyvinyl alcohol Poval MP203 (manufactured by Kuraray Co., Ltd.) were added and thoroughly mixed to prepare a slurry. Zirconia beads (800 g) having an average diameter of 0.5 mm were placed in a vessel with the above slurry and mixed with a disperser (1/4 G sand mill, m.p. provided by Imex Co., Ltd.) for 5 hours, whereby a dispersion of the polyhalo organic compound was obtained. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had an average particle diameter of 0.74 μm.

Preparation of a 10% by weight methanol solution a phthalazine compound:

6-isopropylphthalazine (10 g) was dissolved in 90 g of methanol and used.

Preparation of a 20% by weight Pigment Dispersion:

water (250 g) was added to 64 g C.I. Pigment Blue 60 and 6.4 g of Domol N (prepared from Kao Corporation) and mixed thoroughly to prepare a slurry. Zirconia beads (800 g) with an average diameter of 0.5 mm were placed in a vessel with the above-mentioned slurry and with a disperser (1/4 G sand mill, manufactured by Imex Co., Ltd.) for Dispersed for 25 hours, whereby the pigment dispersion was obtained. The pigment particles contained in the thus obtained pigment dispersion had an average particle diameter of 0.21 μm.

Preparation of a 40 wt .-% - SBR Latex:

By Ultrafiltration of purified SBR latex was obtained as follows.

The SBR latex shown below was 10-fold with distilled water dilute and by means of a module FS03-FC-FUY03A1 for ultrafiltration cleaning (Daisen Membrane System Co., Ltd.) cleaned up the ionic conductivity Reached 1.5 mS / cm. The latex concentration at this time was 40% by weight.

SBR Latex:

Latex of -St (68) -Bu (29) -AA (3) equilibrium moisture content at 25 ° C and 60% relative humidity: 0.6% by weight
average particle size: 0.1 μm
Concentration: 45% by weight
Ion conductivity: 4.2 mS / cm

The ionic conductivity was measured by using a CM-30S conductometer (manufactured by Toa Denpa Kogyo Co., Ltd.), and the starting solution of the latex (40% by weight) was measured at 25 ° C.
pH value: 8.2

Preparation of Emulsion Layer Coating Solution (Photosensitive Layer):

The above-obtained 20% by weight pigment dispersion (1.1 g), 103 g of a dispersion of a silver salt of an organic acid, 5 g of the 20% by weight aqueous solution of the modified polyvinyl alcohol MP-203 (manufactured by Kuraray Co. Ltd.), 25 g of the above prepared 25% by weight reducing agent dispersion, 11.5 g of the 30% by weight dispersion of an organic polyhalogen compound, 3.1 g of the 20% by weight mercapto compound dispersion, 106 g of the 40% by weight ultrafiltration-purified SBR latex and 8 ml of the 10% by weight phthalazine compound solution were mixed together to obtain a solution containing a silver salt of an organic acid. The silver halide grain emulsion (1) (5 g) and the silver halide emulsion (2) (5 g) were thoroughly mixed, stirred for 20 minutes, added with 10 ml of distilled water and with the above solution containing a silver salt of an organic acid immediately before coating with a static mixer to prepare an emulsion layer coating solution. This coating solution was fed as it was in a silver coating amount of 1.4 g / m ^{2 of} a coating die.

The The above emulsion layer coating solution had a viscosity of 85 mPa.s at 40 ° C (Rotor No. 1), measured with a model B viscometer (manufactured from Tokyo Keiki Co., Ltd.).

The viscosity of the coating solution measured by an RFS fluid spectrometer (manufactured by Rheometrics Far East Co.) at 25 ° C was 1,500, 220, 70, 40 and 20 mPa · s at shear rates of 0.1, 1, 10, 100, respectively or 1,000 sec ^-1 .

Preparation of an Interlayer Coating Solution for an Emulsion Surface:

To 772 g of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.) was added an alkali solution (a 20% by weight solution of NH ₄ OH as NH ₄ ⁺ , a 20% by weight solution of LiOH used as Li ⁺ or a 20 wt.% solution of NaOH as Na ⁺ ) in an addition amount as shown in Tables I-1 to I-5, 0.5 g of the 20 wt% pigment dispersion and 226 g of a 27.5% strength by weight solution of a latex of methyl methacrylate / styrene / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio: 59/9/26/5/1), 2 ml of a 5% by weight Aqueous solution of Aerosol OT (manufactured by American Cyanamid Co.) was added to prepare an interlayer coating solution which was coated in a coating amount of 10 ml / m ² .

The viscosity the coating solution was 21 mPa · s at 40 ° C (Rotor # 1) measured with a Model B viscometer.

Production of a first Protective layer coating solution for one Emulsion Surface

Inert gelatin (80 g) was dissolved in water and treated with 0.3 g of the 20% by weight pigment dispersion, a 10% strength by weight phthalic acid methanol solution, 74 ml of a 10% strength by weight aqueous 4-methylphthalic acid solution, 28 ml 1N sulfuric acid and 5 ml of a 5% by weight aqueous solution of Aerosol OT (manufactured by American Cyanamid Co.). Then, water was added to the total amount of 1,000 g, thereby obtaining a first emulsion layer protective layer coating solution coated in a coating amount of 30 ml / m ² .

The viscosity the coating solution was 17 mPa · s at 40 ° C (Rotor # 1) measured with a Model B viscometer. A coating solution was prepared in which polyvinyl alcohol was used instead of gelatin.

Production of a second Protective layer coating solution for an emulsion surface:

Inert gelatin (100 g) was dissolved in water and admixed with 0.2 g of the 20% by weight pigment dispersion, 20 ml of a 5% strength by weight solution of potassium N-perfluorooctylsulfonyl-N-propylalanine, 16 ml of a 5 % By weight solution of Aerosol OT (manufactured by American Cyanamid Co.), 25 g of fine polymethyl methacrylate particles (average particle size: 4.0 μm), 1.4 g of phthalic acid, 1.6 g of 4-methylphthalic acid, 44 ml of 1N Sulfuric acid and 445 ml of a 4 wt -.% Chromalumlösung added. Then, water was added to a total amount of 2,000 g, thereby obtaining a second protective layer coating solution which was coated in a coating amount of 20 ml / m ² .

The viscosity the coating solution was 9 mPa · s at 40 ° C (Rotor # 1) measured with a Model B viscometer. A coating solution was prepared in the polyvinyl alcohol instead of gelatin and boric acid instead Chromalum were used.

Production of a PET carrier:

PET with an intrinsic viscosity IV = 0.66 (measured in phenol / tetrachloroethane, 6/4 by weight, at 25 ° C) was after a conventional Process obtained using terephthalic acid and ethylene glycol. After the obtained PET pelletized and dried for 4 hours at 130 ° C, at 300 ° C melted, over a T-nozzle extruded and suddenly chilled was an unstretched film with a film thickness obtained after the thermal fixation of 175 microns.

The film was stretched with rolls at different peripheral speeds 3.3 times in the machine direction and then 4.5 times with a tenter in the transverse direction. The temperature was 110 ° C or 130 ° C. Subsequently, the film was thermally fixed at 240 ° C for 20 seconds and then relaxed by 4% in the transverse direction at the same temperature. The clamping area of the clamping frame was then slit open and both edges of the film were knurled. The film was wound up at 4 kg / cm ² , whereby a film roll having a thickness of 175 μm was obtained.

Corona discharge treatment the carrier surface:

Both surfaces of the support were brought to room temperature and it was treated with a solid state corona treatment apparatus, Model 6KVA manufactured by Piller Co., at a rate of 20 m / min carried out a corona discharge treatment. From the reading of the electric current density / voltage, the treatment applied to the support was found to be 0.375 kV · A · min / m ² . The treatment frequency was 9.6 kHz and the gap opening between the electrode and the dielectric roller was 1.6 mm.

Preparation of a primed carrier:

(1) Primer: (1-1) Primer coating:

Preparation of the primed carrier:

Both surfaces of the above-prepared biaxially stretched polyethylene terephthalate support having a film thickness of 175 μm were subjected to corona discharge treatment, and then the above primer solution composition (1) was coated with a wire rod in a wet coating amount of 6 ml / m ² (for one surface side) and for 5 minutes dried at 180 ° C. Subsequently, a surface (side of the photosensitive layer) was subjected to a corona discharge treatment, and then the primer solution composition (2) was coated with a wire rod in a wet coating amount of 9 ml / m ² and dried at 180 ° C for 5 minutes. The back surface was coated with the primer solution composition (3) with a wire bar in a wet coating amount of 5 ml / m ² and dried at 180 ° C for 6 minutes. In this way, the primed carrier was prepared.

Preparation of a backside coating solution:

Producing a solid Solid Particle Dispersion Solution (a) a base precursor:

A Base precursor compound shown below (11) (64 g), 28 g of the diphenylsulfone compound (12) shown below and 10 g of the surfactant Demole N (manufactured by Kao Corporation) were mixed with 220 ml of distilled water. The mixed one solution was made using balls in a sand mill (1/4 G sand mill) by Imex Co., Ltd.), whereby a fine particulate solid solution of codispersion (a) is dispersed. the base precursor compound and the diphenylsulfone compound having an average particle size of 0.2 μm has been.

Producing a fine Solid particle dispersion solution of a dye:

The Cyanine dye compound (13) shown below (9.6 g) and 5.8 g Sodium p-alkylbenzenesulfonate was mixed with 305 ml of distilled water mixed. The mixed solution was using beads in a sand mill (1/4 G sand mill, manufactured by Imex Co., Ltd.), whereby a fine solid particle dispersion solution of Dye having an average particle size of 0.2 μm has been.

Preparation of an antihalation coating solution:

PVA-217 (17 g), 9.6 g of polyacrylamide, 70 g of the above fine particle dispersion solid solution (a) of Base precursor, 56 g of the above fine particle dispersion solid solution of the dye, 1.5 g fine polymethyl methacrylate particles (average particle size: 6.5 μm), 2.2 g Sodium polyethylene sulfonate, 0.2 g of a coloring dye compound (14) and 844 ml of water were mixed together. In this way An antihalation coating solution was prepared.

Preparation of Back Surface Protection Layer Coating Solution:

To a reaction kettle maintained at 40 ° C was added 50 g of PVA-117, 0.2 g of sodium polystyrenesulfonate, 2.4 g of N, N'-ethylenebis (vinylsulfonacetamide), 1 g of sodium t-octylphenoxyethoxyethanesulfonate, 30 mg of compound (15). , 32 C ₈ F ₁₇ SO ₃ K mg, 64 mg C8F ₁₇ SO ₂ N (C ₃ H ₇₎ (CH ₂ CH ₂ O) ₄ (CH _{2) 4} -SO ₃ Na, 8.8 g of acrylic acid / ethyl acrylate Copolymer (copolymerization weight ratio: 5/95) and 950 ml of water were added and mixed together to prepare a back surface protective layer coating solution.

Spectral sensitizing dye (1):

Mercapto compound (1):

tellurium:

Base precursor compound (11):

Connection (12):

Cyanine dye compound (13):

Blue dye compound (14):

Compound (15):

Production of a Photothermographic Photosensitive material:

On the back surface of the above primed polyethylene terephthalate support, the halo protective layer coating solution and the back surface protective layer coating solution were simultaneously coated and dried in such a manner that the coated amount of the solid content of the fine dye solid particles of the antihalation coating solution was 0.04 g / m ² and the PVA coating amount of the back surface protective layer coating solution was 1 g / m ² , whereby an antihalation back layer was prepared.

The Emulsion layer, the intermediate layer, the first protective layer and the second protective layer was simultaneously after the sliding ball coating process on the back side layer side opposite Side in this order of the primer side multi-layer coated, whereby a sample of a photothermographic (photosensitive) Material was produced.

The Coating speed was 160 m / min. The distance between the tip of the coating nozzle and the carrier was 0.18 mm. The pressure in the low pressure chamber was at 392 Pa under atmospheric pressure set. In the subsequent cooling zone was air with a Dry bulb temperature of 18 ° C and a wet bulb temperature of 12 ° C for 30 seconds. After drying the coating solution was dry air with a dry bulb temperature of 30 ° C and a wet bulb temperature from 18 ° C inflated in a helical tile drying zone for 200 seconds. The sample was then passed through a drying zone of 70 ° C for 30 seconds passed through and then to 25 ° C cooled, causing the solvent in the coating solution was evaporated. In the cooling zone and in the drying zone was the average wind speed 7 m / sec.

Evaluation of the silver tint by Variation of heat development conditions:

L:

der Unterschied in der Silbertönung durch die Temperaturbedingungen ist gross und nicht praktikabel;

M:

ein Unterschied der Silbertönung durch die Temperaturbedingungen wird beobachtet, ist jedoch in einem zulässigen Bereich;

S:

ein Unterschied der Silbertönung durch die Temperaturbedingungen wird nicht beobachtet und ist gut.

The prepared sample of the photothermographic (photosensitive) material was subjected to stepwise gradation exposure with laser radiation vertically multiplied by using high frequency folding using a semiconductor laser emitting at 660 nm. Then, the heat development for 20 seconds at temperatures of 117 ° C, 120 ° C and 123 ° C with the heat plate heating type apparatus (10) as shown in FIG 1 from JP-A-11-133572, and the difference of the silver tone by the variation of the heat development conditions was evaluated visually according to the following criteria. The sample was odor-neutralized with a metal grid and an activated carbon filter.

L:

the difference in silver tint due to the temperature conditions is large and impractical;

M:

a difference in silver tint due to the temperature conditions is observed but is within a permissible range;

S:

a difference in silver tint due to the temperature conditions is not observed and is good.

• 
  reinschwärzliche Silbertönung, bevorzugt;
• o: leichte Abweichung von Reinschwarz, aber gut
• Δ: eine Spur von Verfärbung ins Purpurfarbene, Blaugrüne oder Gelbe wird beobachtet, akzeptabel;
• Δ*: eine Tönung ins Purpurfarbene, Blaugrüne oder Gelbe wird deutlich beobachtet, ist jedoch akzeptabel;
• x: die Tönung ins Purpurfarbene, Blaugrüne oder Gelbe ist stark, nicht praktikabel.

The silver tint obtained by heat development at 120 ° C for 20 seconds was visually evaluated.

• 
  pure blackish silver tint, preferred;
• o: slight deviation from pure black, but good
• Δ: a trace of discoloration to purple, cyan or yellow is observed, acceptable;
• Δ *: a tint to purple, cyan or yellow is clearly observed, but is acceptable;
• x: the tint in purple, cyan or yellow is strong, not practical.

Evaluation of storage stability:

Of the Difference in Dmin between the prepared photothermographic sample (photosensitive) material for 7 days at 35 ° C and 70 % relative humidity allowed to stand as a coated mass product was, and a sample for 7 days as a coated mass product was measured, was measured. Each sample was subjected to a stepwise gradation exposure with a Semiconductor laser emitted at 660 nm, without a high frequency folding was applied. Then the heat development for 20 Seconds at 120 ° C with the same heat development device (10). The difference in Dmin was as the difference of the measured V value expressed in Macbeth densitometer.

The The results obtained are shown in Tables I-1 to I-5. Tables I-1, I-4 and I-5 show the samples in which Gelatin as main binder in the first and second layers and Tables I-2 and I-3 are the samples shown in which PVA as the main binder in the first and second Layer was used.

TABLE I-1 series in which gelatin was used in the first and second protective layers

TABLE I-2 series was used in the PVA in the first and second protective layers

TABLE I-3 series in which PVA was used in the first and second protective layers

TABLE I-4 series in which PVA was used in the first and second protective layers

Out the results of Tables I-1, I-2, I-3, I-4 and I-5 is the invention Effect visible. The inventive samples are with respect to their photographic properties excellent.

EXAMPLE I-2

Samples were prepared in the same manner as in Example I-1 except that the SBR latex used in the emulsion layers was not cleaned. The same results were obtained as in Example I-1 scored.

EXAMPLE I-3

In samples were prepared in the same way as in Example I-1, except that the latices Lb1 and Lc1 (equilibrium moisture content at 25 ° C and 60 relative humidity was smaller in Lb1 and Lc1, respectively as 2% by weight) as shown below instead of in the emulsion layers used SBR latex were used. There were the same results achieved as in Example I-1.

Synthesis of Lb1:

In a glass autoclave (TEM-V1000, manufactured by Taiatsu Glass Kogyo Co., Ltd.) were added 140 g of styrene, 280 g of distilled water, 4.44 g g of a surfactant (Sandet BL, manufactured by Sanyo Kasei Co., Ltd.) and 6 g of acrylic acid given and the content was for Stirred for 1 hour in a nitrogen atmosphere. Subsequently, 54 g of 2-ethylhexyl acrylate was added to the reaction mixture and the Temperature was at 70 ° C raised. Then, 20 g of a 5% by weight aqueous ammonium persulfate solution was added and stirring was for Continued for 10 hours. Upon completion of the stirring, the temperature became in the reaction vessel lowered to room temperature, thereby obtaining a styrene-acrylic latex has been. To this latex was added to adjust the pH to 7.5 1 N aqueous Ammonia added.

On this way became the latex Lb1 having an average particle diameter of 98 nm and a concentration of 42 wt. Obtained. The equilibrium moisture content of the polymer at 25 ° C and 60% relative humidity was 0.7% by weight.

Synthesis of Lc1:

In an autoclave (TEM-V1000, manufactured by Taiatsu Glass Kogyo Co., Ltd.), 126 g of methyl methacrylate, 280 g of distilled water, 8.2 g of a surfactant (Sandet BL, manufactured by Sanyo Kasei Co., Ltd.) and 4 g of acrylic acid given and the content was for Stirred for 1 hour in a nitrogen atmosphere. Then, 70 g of ethyl acrylate was added to the reaction mixture and the temperature was raised to Raised to 60 ° C. Then, 20 g of a 5 wt% aqueous potassium persulfate solution was added and stirring was for Continued for 10 hours. Upon completion of the stirring, the temperature became the reaction vessel lowered to room temperature, creating an acrylic latex was obtained. This latex was used to adjust the pH to 7.5 1 N aqueous Ammonia added.

On this way became latex Lc1 with an average particle diameter of 101 nm and a concentration of 44% by weight. The equilibrium moisture content of the polymer at 25 ° C and 60% relative humidity was 0.7% by weight.

EXAMPLE I-4

In In the same manner as in Examples I-1 to I-3, samples were made except that the photosensitive silver halide is omitted has been. The obtained samples were thermosensitive with a thermal head Type at 100 ° C or more heated (Maximum temperature: 230 ° C). The same results as in Examples I-1 to I-3 received.

EXAMPLE II-1

Preparation of silver halide grains (1):

To 1.421 ml of distilled water were added 6.7 ml of a 1% by weight potassium bromide solution, 8.2 ml of 1N nitric acid and 21.8 g of phthalated gelatin. This mixed solution was stirred in a titanium-coated stainless reaction vessel while maintaining a temperature of 25 ° C. The solution (a1) (37.4 g of silver nitrate diluted to 159 ml with distilled water) and the solution (b1) (32.6 g of potassium bromide diluted to 200 ml with distilled water) were prepared. The total amount of the solution (a1) was added to the reaction vessel at a constant flow rate by a controlled double jet method while maintaining a pAg of 8.1 within 1 minute (solution (b1) was added by a controlled double jet method). Then, 30 ml of a 3.5 wt% aqueous hydrogen peroxide solution and further 33.6 ml of a 3 wt% aqueous benzimidazole solution were added. The solutions (a2) (solution (a1) were redissolved with distilled water Diluted 317.5 ml) and (b2) (dipotassium hexachloroiridate was dissolved in solution (b1) so that the concentration was 1 × 10 ^-4 mol per mol of silver, and with distilled water to a final volume of 2 times solution (b1 ), ie 400 ml, diluted). The total amount of solution (a2) was added to the reaction vessel at a constant flow rate by a controlled double jet method while maintaining a pAg of 8.1 within 10 minutes (solution (b2) was added by a controlled double jet method). Then, 50 ml of a 0.5 wt% methanol solution of 2-mercapto-5-methylbenzimidazole was added, and further, the pAg was lowered to 7.5 with silver nitrate, and the pH was adjusted to 3.8 with 1 N sulfuric acid set and stop stirring. The reaction solution was subjected to precipitation, desalting and washing processes, then 3.5 g of deionized gelatin and then 1N sodium hydroxide were added, bringing the pH to 6.0 and the pAg. was adjusted to 8.2, whereby a silver halide dispersion was obtained.

The grains in the thus prepared silver halide emulsion were pure silver bromide grains with an average sphere equivalent diameter of 0.031 μm and a sphere equivalent diameter variation coefficient of 11%. The grain size was the average of 1,000 grains, measured with an electron microscope. The (100) area ratio of these grains was 85% by the Kubelka-Munk method.

The temperature of the above emulsion was raised to 45 ° C with stirring and then 5 ml of a 0.5% by weight methanol solution of N, N'-dihydroxy-N ", N" -diethylmelamine and 5 ml of a 3 , 5 wt.% Methanol solution of phenoxyethanol, and 1 minute later, 3 × 10 ^-5 mol per mol of silver sodium benzenethiosulfonate.

Another 2 minutes thereafter, a solid dispersion of the spectral sensitizing dye (1) (an aqueous gelatin solution) was added in an amount of 5 × 10 ^-3 mol per mol of silver, and another 2 minutes thereafter, 5 × 10 ^-5 mol per mol of silver of a tellurium compound added and the reaction solution matured for 50 minutes. Immediately before completion of the ripening, 2-mercapto-5-methylbenzimidazole in an amount of 1 x 10 ^-3 mol and mercapto compound (1) in an amount of 1.1 x 10 ^-3 mol, each per mol of silver, were added to the reaction solution , The temperature was lowered to 32 ° C. In this way, the silver halide grain emulsion (1) was prepared.

Preparation of silver halide grains ( 2 ):

Phthalated gelatin (22 g) and 30 mg of potassium bromide were dissolved in 700 ml of water, and the pH was adjusted to 5.0 at 35 ° C. An aqueous solution (159 ml) containing 18.6 g of silver nitrate and 0.9 g of ammonium nitrate and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 92/8 were immersed by a controlled double jet method within 10 minutes Maintaining a pAg of 7.7 added to the aforementioned solution. Subsequently, 476 ml of an aqueous solution containing 55.4 g of silver nitrate and 2 g of ammonium nitrate and an aqueous solution containing 1 × 10 ^-5 mol / liter of dipotassium hexachloroiridate and 1 mol / liter of potassium bromide were added to the above-mentioned solution in a controlled manner Double jet method was added within 30 minutes, keeping the pAg at 7.7. Subsequently, 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added, the pH was lowered and the reaction solution subjected to coagulant precipitation and desalted. Then, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 8.2, thereby completing the production of silver iodobromide grains. The silver halide grains thus obtained were cubic grains having an iodine content in the core region of 8 mol% and an average of 2 mol%, an average grain size of 0.005 μm, a variation coefficient of the projected area diameter of 8% and a (100) area ratio of 88%. ,

The temperature of the silver halide grains thus obtained was raised to 60 ° C. To the above silver halide grains were added sodium thiosulfate (85 μmol), 1.1 x 10 ^-5 mol of 2,3,4,5,6-pentafluorophenylphosphine selenide, 1.5 x 10 ^-5 mol of a tellurium compound, 3.5 x 10 ^-8 mol Chloroauric acid and 2.7 x 10 ^-4 moles of thiocyanic acid, each per mole of silver, and then ripened for 120 minutes and then cooled to 40 ° C. Then, the spectral sensitizing dye (1) was added in an amount of 1 × 10 ^-4 mol and 2-mercapto-5-methylbenzimidazole in an amount of 5 × 10 ^-4 mol, and then the solution was cooled to 30 ° C, whereby the Silver halide emulsion (2) was obtained.

manufacturing of a scale-like fatty acid silver salt:

Behenic acid (87.6 g) (manufactured by Henkel Co., trade name Edenor C22-85R), 423 ml distilled Water, 49.2 ml of an aqueous solution containing 5N NaOH and 120 ml of t-butanol were mixed together, and the mixture was reacted at 75 ° C for 1 hour to obtain a sodium behenate solution. Separately from the sodium behenate solution, 206.2 ml of an aqueous solution containing 40.4 g of silver nitrate (pH 4.0) was prepared and kept at 10 ° C. A reaction vessel containing 635 ml of distilled water and 30 ml of t-butanol was kept at 30 ° C while stirring the contents of the reaction vessel, the entire amount of the above sodium behenate solution and the whole amount of the aqueous silver nitrate solution were stirred at a constant flow rate within Added to the reaction vessel for 62 minutes and 10 seconds and 60 minutes, respectively, in such a manner that only the aqueous silver nitrate solution was added from the beginning of the addition, the addition of the sodium behenate solution was started 7 minutes and 20 seconds after the start of the addition of the aqueous silver nitrate solution and after completion of the addition of the aqueous silver nitrate solution, only the sodium behenate solution was added for 9 minutes and 30 seconds. The temperature in the reaction vessel was kept at 30 ° C and the outside temperature was controlled so that the temperature did not increase. The tubes of the addition system of the sodium behenate solution were heated by a steam heating jacket method and the steam inlet opening was adjusted so that the solution temperature at the outlet of the addition nozzle tip was 75 ° C. The piping system of the aqueous silver nitrate solution addition system was heated by circulating cooling water in the outer tube of the double pipe. The positions to which the sodium behenate solution and the aqueous silver nitrate solution were added were symmetrically placed with respect to the intervening stirring axis, and the height of the position was adjusted so that the reaction solution was not touched.

To Completion of the addition of the sodium behenate solution became the reaction solution the same temperature for Stirred for 20 minutes and then allowed to lower the temperature to 25 ° C. The solids content was then separated by suction filtration. The solids content was washed with water until the conductivity of the filtrate reached 30 μS / cm. In this way, a fatty acid silver salt was obtained. Of the The solid content obtained was not dried and used as a wet cake stored.

The Shape of the obtained silver behenate particles was measured by an electron microscope examined. The obtained silver behenate particles were scale-like Crystals with a = 0.14 μm, b = 0.4 μm and c = 0.6 μm im Average, and the coefficient of variation of the average Equivalent spherical diameter was 15%.

polyvinyl alcohol (Brand name: PVA-217) (7.4 g) and water became the wet cake in an amount corresponding to 100 g of dried solids, to a total of 385 g was added and then temporarily in a homomixer dispersed.

The preliminarily dispersed starting solution was dispersed three times using a disperser (trade name: Microfluidizer M-1105-EH equipped with a G10Z interaction chamber, manufactured by Micro Fluidex International Corp.). The pressure of the disperser was set at 1750 kg / cm ² . In this way, a silver behenate dispersion was obtained. The cooling operation was performed by installing heat exchange coils, respectively before and after the interaction chamber, and adjusting the desired dispersion temperature by adjusting the temperature of the cooling medium.

Preparation of acicular fatty acid silver salt (Comparison):

Under stir were 43.8 g of behenic acid (manufactured by Henkel Co., trade name: Edenor C22-85R), 730 ml distilled water and 60 ml of t-butanol of 79 ° C with 117 ml of an aqueous Solution, containing 1 N NaOH, over Staggered 55 minutes and the mixture was reacted for 240 minutes. Then were 112.5 ml of an aqueous Solution, containing 19.2 g of silver nitrate was added within 45 seconds and the solution was for Allowed to stand for 20 minutes, which lowered the temperature to 30 ° C. has been. The solids content was then separated by suction filtration. The solids content was washed with water until the conductivity of the filtrate 30 μS / cm reached. The solids content thus obtained was not dried and treated as a wet cake. Polyvinyl alcohol (brand name: PVA-205) (7.4 g) and water were added to the wet cake in an amount that 100 g of dried solids corresponded to a total amount of 385 g was added and then preliminarily dispersed in a homomixer.

The preliminarily dispersed starting solution was treated three times using a disperser (trade name: Microfluidizer M-110S-EH equipped with a G10Z interaction chamber manufactured by Micro Fluidex International Corp.). The pressure of the disperser was set at 1750 kg / cm ² . In this way, the silver behenate dispersion (B) was obtained. The silver behenate particles contained in the silver behenate dispersion thus obtained were acicular particles of a = 0.04 μm, b = 0.04 μm and c = 0.8 μm on average and a coefficient of variation of 30%. The particle size was measured by Master Sizer X (manufactured by Malvern Instruments Ltd.). The cooling was performed by installing coil-shaped heat exchangers respectively before and after the interaction chamber, and adjusting the desired temperature of the dispersion by adjusting the temperature of the cooling medium.

Preparation of a 25 wt .-% - Reducing agent dispersion:

water (176 g) was added to 80 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 64 g of a 20% by weight aqueous solution solution of the modified polyvinyl alcohol Poval MP203 (manufactured by Kuraray Co., Ltd.) was added and thoroughly mixed to prepare a slurry. Zirconia beads (800 g) with an average diameter of 0.5 mm were in a vessel with the above slurry added and with a disperser (1/4 G sand mill, produced from Imex Co., Ltd.) for Dispersed for 5 hours, whereby the reducing agent dispersion obtained has been. The particles of the reduction agent dispersion thus obtained contained reducing agent had an average particle diameter of 0.72 μm.

Preparation of a 10% by weight methanol solution the mercapto compound:

10 g of 3-mercapto-4-phenyl-5-heptyl-1,2,4-triazole were dissolved in 90 g of methanol dissolved.

Preparation of a 20% by weight Dispersion of a mercapto compound:

water (224 g) was added to 64 g of 3-mercapto-4-phenyl-5-heptyl-1,2,4-triazole and 32 g of a 20% strength by weight solution of the modified polyvinyl alcohol Poval MP203 (manufactured by Kuraray Co., Ltd.) was added and thoroughly mixed to prepare a slurry. Zirconia beads (800 g) with an average diameter of 0.5 mm were in a vessel with the above slurry and with a disperser (1/4 G sand mill, manufactured by Imex Co., Ltd.) for Dispersed for 10 hours, whereby the Mercaptoverbindungsdispersion was obtained. The particles of the mercapto compound dispersion thus obtained contained mercapto compound had an average particle diameter of 0.67 μm.

Preparation of a 30 wt .-% - Dispersion of an organic polyhalogen compound:

water (224 g) was added to 44 g of tribromomethylphenylsulfone, 44 g of 3-tribromomethylsulfonyl-4-phenyl-5-tridecyl-1,2,4-triazole, 8 g of tribromomethyl-4- (2,4,6-trimethylphenylsulfonyl) phenylsulfone, 0.8 g of sodium triisopropyl-α-naphthalenesulfonate and 48 g of a 20% by weight aqueous solution solution of the modified polyvinyl alcohol Poval MP203 (manufactured by Kuraray Co., Ltd.) was added and thoroughly mixed to prepare a slurry. Zirconia beads (800 g) with an average diameter of 0.5 mm were placed in a vessel with the above slurry and with a disperser (1/4 G sand mill, manufactured by Imex Co., Ltd.) for 5 hours, whereby a dispersion of the organic polyhalogen compound was obtained. The particles of the organic polyhalogen compound, contained in the polyhalogen compound dispersion thus obtained were, had an average particle diameter of 0.74 microns.

Preparation of a 10% by weight methanol solution a phthalazine compound:

6-isopropylphthalazine (10 g) was dissolved in 90 g of methanol and used.

Preparation of a 20% by weight Pigment Dispersion:

water (240 g) was added to 64 g C.I. Pigment Blue 60 and 6.4 g of Domol N (prepared from Kao Corporation) and mixed thoroughly to prepare a slurry. Zirconia beads (800 g) with an average diameter of 0.5 mm were placed in a vessel with the above-mentioned slurry and with a disperser (1/4 G sand mill, manufactured by Imex Co., Ltd.) for Dispersed for 25 hours, whereby the pigment dispersion was obtained. The pigment particles contained in the thus obtained pigment dispersion had an average particle diameter of 0.21 μm.

Preparation of a 40 wt .-% - SBR Latex:

By Ultrafiltration of purified SBR latex was obtained as follows.

The SBR latex shown below was 10-fold with distilled water dilute and by means of a module FS03-FC-FUY03A1 for ultrafiltration cleaning (Daisen Membrane System Co., Ltd.) cleaned up the ionic conductivity Reached 1.5 mS / cm. The latex concentration at this time was 40% by weight.

SBR Latex:

Latex of -St (68) -Bu (29) -AA (3) equilibrium moisture content at 25 ° C and 60%
relative humidity: 0.6% by weight
average particle size: 0.1 μm
Concentration: 45% by weight
Ion conductivity: 4.2 mS / cm

The ionic conductivity was measured by using a CM-30S conductometer (manufactured by Toa Denpa Kogyo Co., Ltd.), and the starting solution of the latex (40% by weight) was measured at 25 ° C.
pH value: 8.2

Preparation of Emulsion Layer Coating Solution (Photosensitive Layer):

The above-obtained 20% by weight pigment dispersion (1.1 g), 103 g of a dispersion of a silver salt of an organic acid, 5 g of the 20% by weight aqueous solution of the modified polyvinyl alcohol MP-203 (manufactured by Kuraray Co. Ltd.), 25 g of the above prepared 25% by weight reducing agent dispersion, 11.5 g of the 30% by weight dispersion of an organic polyhalogen compound, 3.1 g of the 20% by weight mercapto compound dispersion, 106 g of the 40% by weight ultrafiltration-purified SBR latex and 8 ml of the 10% by weight phthalazine compound solution were mixed together to obtain a solution containing a silver salt of an organic acid. The silver halide grain emulsion (1) (5 g) and the silver halide emulsion (2) (5 g) were thoroughly mixed, stirred for 20 minutes, added with 10 ml of distilled water and with the above solution containing a silver salt of an organic acid immediately before coating with a static mixer to prepare an emulsion layer coating solution. This coating solution was fed as it was in a silver coating amount of 1.4 g / m ^{2 of} a coating die.

The The above emulsion layer coating solution had a viscosity of 85 mPa.s at 40 ° C (Rotor No. 1), measured with a model B viscometer (manufactured from Tokyo Keiki Co., Ltd.).

The viscosity of the coating solution measured by an RFS fluid spectrometer (manufactured by Rheometrics Far East Co.) at 25 ° C was 1,500, 220, 70, 40 and 20 mPa · s at shear rates of 0.1, 1, 10, 100, respectively or 1,000 sec ^-1 .

manufacturing an interlayer coating solution for an emulsion surface:

To 772 g of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.), 0.5 g of the 20% by weight pigment dispersion and 226 g of a 27.5% by weight solution of a latex of methyl methacrylate / styrene / 2-Ethylhexyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio: 59/9/26/5/1) was added to 2 ml of a 5 wt% aqueous solution of Aerosol OT (manufactured by American Cyanamid Co.) to obtain a Interlayer coating solution was prepared, which was coated in a coating amount of 10 ml / m ² .

The viscosity the coating solution was 21 mPa · s at 40 ° C (Rotor # 1) measured with a Model B viscometer.

Production of a first Protective layer coating solution for one Emulsion Surface

Inert gelatin (80 g) was dissolved in water and 6 g of a tinting agent (shown in Tables II-1 and II-2), 0.3 g of the 20% by weight pigment dispersion, 28 ml of 1 N sulfuric acid and 5 ml A 5% by weight aqueous solution of Aerosol OT (manufactured by American Cyanamid Co.) was added thereto. Then, water was added to the total amount of 1,000 g, thereby obtaining a first emulsion layer protective layer coating solution coated in a coating amount of 30 ml / m ² .

The viscosity of the coating solution was 17 mPa · s at 40 ° C (rotor No. 1) measured with a Model B viscometer. A coating solution was prepared in which polyvinyl alcohol was used instead of gelatin.

Production of a second Protective layer coating solution for an emulsion surface:

Inert gelatin (100 g) was dissolved in water and admixed with 0.2 g of the 20% by weight pigment dispersion, 20 ml of a 5% strength by weight solution of potassium N-perfluorooctylsulfonyl-N-propylalanine, 16 ml of a 5 % By weight solution of Aerosol OT (manufactured by American Cyanamid Co.), 25 g of polymethyl methacrylate fine particles (average particle size: 4.0 μm), 44 ml of 1N sulfuric acid and 445 ml of a 4% by weight chromium solution. Then, water was added to a total amount of 2,000 g, thereby obtaining a second protective layer coating solution which was coated in a coating amount of 20 ml / m ² .

The viscosity the coating solution was 9 mPa · s at 40 ° C (Rotor # 1) measured with a Model B viscometer. A coating solution was prepared in the polyvinyl alcohol instead of gelatin and boric acid instead Chromalum were used.

Production of a PET carrier:

PET with an intrinsic viscosity IV = 0.66 (measured in phenol / tetrachloroethane, 6/4 by weight, at 25 ° C) was after a conventional Process obtained using terephthalic acid and ethylene glycol. After the obtained PET pelletized and dried for 4 hours at 130 ° C, at 300 ° C melted, over a T-nozzle extruded and suddenly chilled was an unstretched film with a film thickness obtained after the thermal fixation of 175 microns.

The film was stretched with rolls at different peripheral speeds 3.3 times in the machine direction and then 4.5 times with a tenter in the transverse direction. The temperature was 110 ° C or 130 ° C. Subsequently, the film was thermally fixed at 240 ° C for 20 seconds and then relaxed by 4% in the transverse direction at the same temperature. The clamping area of the clamping frame was then slit open and both edges of the film were knurled. The film was wound up at 4 kg / cm ² , whereby a film roll having a thickness of 175 μm was obtained.

Corona discharge treatment the carrier surface:

Both surfaces of the support were brought to room temperature, and a corona discharge treatment was carried out with a solid state corona treatment apparatus, model 6KVA manufactured by Piller Co., at a speed of 20 m / min. From the reading of the electric current density / voltage, the treatment applied to the support was found to be 0.375 kV · A · min / m ² . The treatment frequency was 9.6 kHz and the gap opening between the electrode and the dielectric roller was 1.6 mm.

Preparation of primed support: (1) Primer: (1-1) Primer coat:

Preparation of the primed carrier:

Both surfaces of the above-prepared biaxially stretched polyethylene terephthalate support having a film thickness of 175 μm were subjected to corona discharge treatment, and then the above primer solution composition (1) was coated with a wire rod in a wet coating amount of 6 ml / m ² (for one surface side) and for 5 minutes dried at 180 ° C. Subsequently, a surface (side of the photosensitive layer) was subjected to a corona discharge treatment, and then the primer solution composition (2) was coated with a wire rod in a wet coating amount of 9 ml / m ² and dried at 180 ° C for 5 minutes. The back surface was coated with the primer solution composition (3) with a wire bar in a wet coating amount of 5 ml / m ² and dried at 180 ° C for 6 minutes. In this way, the primed carrier was prepared.

Preparation of a backside coating solution:

Producing a solid Solid Particle Dispersion Solution (a) a base precursor:

A Base precursor compound shown below (11) (64 g), 28 g of the diphenylsulfone compound (12) shown below and 10 g of the surfactant Demole N (manufactured by Kao Corporation) were mixed with 220 ml of distilled water. The mixed one solution was made using balls in a sand mill (1/4 G sand mill) by Imex Co., Ltd.), whereby a fine particulate solid solution of codispersion (a) is dispersed. the base precursor compound and the diphenylsulfone compound having an average particle size of 0.2 μm has been.

Producing a fine Solid particle dispersion solution of a dye:

The Cyanine dye compound (13) shown below (9.6 g) and 5.8 g Sodium p-alkylbenzenesulfonate was mixed with 305 ml of distilled water mixed. The mixed solution was using beads in a sand mill (1/4 G sand mill, manufactured by Imex Co., Ltd.), whereby a fine solid particle dispersion solution of Dye having an average particle size of 0.2 μm has been.

Preparation of an antihalation coating solution:

PVA-217 (17 g), 9.6 g of polyacrylamide, 70 g of the above fine particle dispersion solid solution (a) of Base precursor, 56 g of the above fine particle dispersion solid solution of the dye, 1.5 g fine polymethyl methacrylate particles (average particle size: 6.5 μm), 2.2 g Sodium polyethylene sulfonate, 0.2 g of a coloring dye compound (14) and 844 ml of water were mixed together. In this way An antihalation coating solution was prepared.

Preparation of Back Surface Protection Layer Coating Solution:

To a reaction kettle maintained at 40 ° C was added 50 g of PVA-117, 0.2 g of sodium polystyrenesulfonate, 2.4 g of N, N'-ethylenebis (vinylsulfonacetamide), 1 g of sodium t-octylphenoxyethoxyethanesulfonate, 30 mg of compound (15). , 32 mg C ₈ F ₁₇ SO ₃ K, 64 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ -SO ₃ Na, 8.8 g acrylic acid / Ethyl acrylate copolymer (copolymerization weight ratio: 5/95) and 950 ml of water were added and mixed together to prepare a back surface protective layer coating solution.

Spectral sensitizing dye (1):

Mercapto compound (1):

tellurium:

Base precursor compound (11):

Connection (12):

Cyanine dye compound (13):

Blue dye compound (14):

Compound (15):

Production of a Photothermographic Photosensitive material:

On the back surface of the above primed polyethylene terephthalate support, the halo protective layer coating solution and the back surface protective layer coating solution were simultaneously coated and dried in such a manner that the coated amount of the solid content of the fine dye solid particles of the antihalation coating solution was 0.04 g / m ² and the PVA coating amount of the back surface protective layer coating solution was 1 g / m ² , whereby an antihalation back layer was prepared.

The Emulsion layer, the intermediate layer, the first protective layer and the second protective layer was simultaneously after the sliding ball coating process on the back side layer side opposite Side in this order of the primer side multi-layer coated, whereby a sample of a photothermographic (photosensitive) Material was produced.

The Coating speed was 160 m / min. The distance between the tip of the coating nozzle and the carrier was 0.18 mm. The pressure in the low pressure chamber was at 392 Pa under atmospheric pressure set. In the subsequent cooling zone was air with a Dry bulb temperature of 18 ° C and a wet bulb temperature of 12 ° C for 30 seconds. After drying the coating solution was dry air with a dry bulb temperature of 30 ° C and a wet bulb temperature from 18 ° C inflated in a helical tile drying zone for 200 seconds. The sample was then passed through a drying zone of 70 ° C for 30 seconds passed through and then to 25 ° C cooled, causing the solvent in the coating solution was evaporated. In the cooling zone and in the drying zone was the average wind speed 7 m / sec.

Evaluation of the silver tint by Variation of heat development conditions:

L:

der Unterschied in der Silbertönung durch die Temperaturbedingungen ist gross und nicht praktikabel;

M:

ein Unterschied der Silbertönung durch die Temperaturbedingungen wird beobachtet, ist jedoch in einem zulässigen Bereich;

S:

ein Unterschied der Silbertönung durch die Temperaturbedingungen wird nicht beobachtet und ist gut.

The prepared sample of the photothermographic (photosensitive) material was subjected to stepwise gradation exposure with laser radiation vertically multiplied by using high frequency folding using a semiconductor laser emitting at 660 nm. Then, the heat development for 20 seconds at temperatures of 117 ° C, 120 ° C and 123 ° C with the heat plate heating type apparatus (10) as shown in FIG 1 from JP-A-11-133572, and the difference of the silver tone by the variation of the heat development conditions was evaluated visually according to the following criteria. The sample was odor-neutralized with a metal grid and an activated carbon filter.

L:

the difference in silver tint due to the temperature conditions is large and impractical;

M:

a difference in silver tint due to the temperature conditions is observed but is within a permissible range;

S:

a difference in silver tint due to the temperature conditions is not observed and is good.

Evaluation of storage stability:

Of the Difference in Dmin between the prepared photothermographic sample (photosensitive) material for 7 days at 35 ° C and 70 % relative humidity allowed to stand as a coated mass product was, and a sample for 7 days as a coated mass product was measured, was measured. Each sample was subjected to a stepwise gradation exposure with a Semiconductor laser emitted at 660 nm, without a high frequency folding was applied. Then the heat development for 20 Seconds at 120 ° C with the same heat development device (10). The difference in Dmin was as the difference of the measured V value expressed in Macbeth densitometer.

The The results obtained are shown in Tables II-1 and II-2. Table II-1 shows the samples in which gelatin is the major binder was used in the first and second layers, and in Table II-2, the samples are shown in which PVA as the main binder was used in the first and second layers.

TABLE II-1 series in which gelatin was used in the first and second protective layers

CONTINUATION TABLE II-1 series in which gelatin was used in the first and second protective layers

TABLE II-2 series in which PVA was used in the first and second protective layers

Out the results of Tables II-1 and II-2 is the inventive effect seen. The inventive Samples are re Their photographic properties are excellent.

EXAMPLE II-2

In the same manner as in Example II-1, samples were prepared except that the content of stearic acid was changed (as shown in Table II-3) when the flaky silver salt of an organic acid was prepared, and were prepared in the same manner as in Example II-1 evaluated. The results obtained are shown in Table II-3. In each sample, PVA was used as the major binder in the first and second th protective layer used.

TABLE II-3 series in which PVA was used in the first and second protective layers

CONTINUATION TABLE II-3 series in which PVA was used in the first and second protective layers

The Results in Table II-3 show that storage stability by increase the content of silver behenate is improved.

EXAMPLE II-3

In In the same manner as in Examples II-1 and II-2, samples were made except that used in the emulsion layers SBR latex was not cleaned.

It were the same results as in Examples II-1 and II-2 achieved.

EXAMPLE II-4

In samples were prepared in the same way as in Example II-1, except that the latices Lb1 and Lc1 (equilibrium moisture content at 25 ° C and 60 relative humidity was lower in Lb1 and Lc1, respectively as 2% by weight) as shown below instead of in the emulsion layers used SBR latex were used. There were the same results achieved as in Example II-1.

Synthesis of Lb1:

In a glass autoclave (TEM-V1000, manufactured by Taiatsu Glass Kogyo Co., Ltd.) were added 140 g of styrene, 280 g of distilled water, 4.44 g g of a surfactant (Sandet BL, manufactured by Sanyo Kasei Co., Ltd.) and 6 g of acrylic acid given and the content was for Stirred for 1 hour in a nitrogen atmosphere. Subsequently, 54 g of 2-ethylhexyl acrylate was added to the reaction mixture and the Temperature was at 70 ° C raised. Then, 20 g of a 5% by weight aqueous ammonium persulfate solution was added and stirring was for Continued for 10 hours. Upon completion of the stirring, the temperature became in the reaction vessel lowered to room temperature, thereby obtaining a styrene-acrylic latex has been. To this latex was added to adjust the pH to 7.5 1 N aqueous Ammonia added.

On this way became the latex Lb1 having an average particle diameter of 98 nm and a concentration of 42 wt. Obtained. The equilibrium moisture content of the polymer at 25 ° C and 60% relative humidity was 0.7% by weight.

Synthesis of Lc1:

In an autoclave (TEM-V1000, manufactured by Taiatsu Glass Kogyo Co., Ltd.), 126 g of methyl methacrylate, 280 g of distilled water, 8.2 g of a surfactant (Sandet BL, manufactured by Sanyo Kasei Co., Ltd.) and 4 g of acrylic acid given and the content was for Stirred for 1 hour in a nitrogen atmosphere. Then, 70 g of ethyl acrylate was added to the reaction mixture and the temperature was raised to Raised to 60 ° C. Then, 20 g of a 5 wt% aqueous potassium persulfate solution was added and stirring was for Continued for 10 hours. Upon completion of the stirring, the temperature became the reaction vessel lowered to room temperature, creating an acrylic latex was obtained. This latex was used to adjust the pH to 7.5 1 N aqueous Ammonia added.

On this way became latex Lc1 with an average particle diameter of 101 nm and a concentration of 44% by weight. The equilibrium moisture content of the polymer at 25 ° C and 60% relative humidity was 0.7% by weight.

EXAMPLE II-5

In In the same manner as in Examples II-1 to II-4, samples were made except that the photosensitive silver halide is omitted has been. The obtained samples were thermosensitive with a thermal head Type (maximum temperature: 230 ° C) at 100 ° C or more heated. The same results as in Examples II-1 to II-4 received.

EFFECT OF THE INVENTION:

To the inventive Procedures can the storage stability a coated mass product and the silver tint improved become.

Claims (14)

An image-recording material comprising at least on a surface side of a support a thermosensitive recording element containing: a scale-like silver salt of an organic acid, wherein the term "scale-like silver salt of an organic acid" means a silver salt of an organic acid having a shape approximating a rectangular parallelepiped; means, and if the sides of the rectangular parallelepiped are assumed to be a, b and c starting from the shortest ones (c can be equal to b), x is calculated from the shorter numerical values a and b as follows: x = b / a x is obtained for about 200 particles by the above equation, and when the average value is taken as x (average), those are considered as scale-like particles satisfying the relationship x (average)> 1.5, a reducing agent for silver ion and a binder, or a photosensitive recording element containing: a scale-like silver salt of an organic acid, a reducing agent for a silver ion, photosensitive silver halide and a binder, wherein the NH ₄ ⁺ content of all the layers on the surface side of the support having the thermosensitive or photosensitive recording element is from 0.06 to 3.4 mmol as the coated amount per m ^{2 of} the support. An image-recording material comprising at least on a surface side of a support a thermosensitive recording element containing: a scale-like silver salt of an organic acid, wherein the term "scale-like silver salt of an organic acid" means a silver salt of an organic acid having a shape approximating a rectangular parallelepiped; means, and if the sides of the rectangular parallelepiped are assumed to be a, b and c starting from the shortest one (c can be equal to b), x is calculated from the shorter numerical values a and b as follows: x = b / a x is obtained for about 200 particles by the above equation, and when the average value is taken as x (average), those are considered as scale-like particles satisfying the relationship x (average)> 1.5, a reducing agent for silver ion and a binder, or a photosensitive recording element containing: a scale-like silver salt of an organic acid, a reducing agent for a silver ion, photosensitive silver halide and a binder, wherein the alkali metal ion content of all the layers on the surface side of the support having the thermosensitive or photosensitive recording element, from 0.05 to 3.6 mmol as coating amount per m ^{2 of} the carrier. An image-recording material according to claims 1 and 2, wherein the ratio of the contents of alkali metal ion and NH ₄ ^{+ is} a molar ratio (NH ₄ ⁺ ) / (alkali metal ion) of 0.01-30. A material as claimed in claim 1 or 3, wherein the NH ₄ ⁺ content is 0.55-2.8 mmol as the coated amount per m ^{2 of} the carrier. A material as claimed in claim 2 or 3, wherein the alkali metal ion content is 0.59-3.0 mmol as the coated amount per m ^{2 of} the carrier. A material as claimed in any one of claims 2, 3 and 5 wherein the alkali metal ion is Li ⁺ , Na ⁺ or K ⁺ . A material as claimed in claim 3, wherein the ratio of (NH ₄ ⁺ ) / (alkali metal ion) is 0.1-20. A material as claimed in claim 3, wherein the ratio of (NH ₄ ⁺ ) / (alkali metal ion) is 0.5-5. A material as claimed in any one of claims 1 to 8, wherein the layer containing a scale-like silver salt of an organic acid further contains a phthalic acid compound represented by formula (I):

wherein R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a monovalent substituent; L ₁ and L ₂ each represent a linking group; n1 and n2 are each 0 or 1; M represents a hydrogen atom or a counterion; and k represents a valence of M, and when M represents a hydrogen atom, k is 1, provided that when M represents a hydrogen atom and n1 and n2 are each 0, not all R ₁ , R ₂ , R ₃ and R _{4 represent} a hydrogen atom are. A material as claimed in claim 9 wherein M in formula (I) is an ammonium ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a zinc ion, an ionic polymer, an organic compound with represents an opposite charge or a metal complex ion. A material as claimed in any one of claims 1 to 10 wherein the content of silver behenate of the silver salt of the organic acid is 92 mol% or more. A material as claimed in any one of claims 1 to 11, wherein the layer containing the scale-like silver salt of an organic Contains acid, formed is by coating a coating solution, wherein 30% by weight or more of the solvent are occupied by water, and then drying, and the main binder This layer is a polymer with an equilibrium moisture content at 25 ° C, 60% RH is 2% by weight or less. A material as claimed in any one of claims 1 to 12 wherein the material contains a photosensitive recording element. A material as claimed in claim 13, wherein the material has two or more constitutional layers, the photosensitive recording element on the same surface side of the carrier on which provided the photosensitive recording element and these two or more constitutional layers at the same time are applied.