Photothermographic material

TECHNICAL FIELD

[0001] The present invention relates to a photothermographic material, in particular, a photothermographic material for scanners and image setters, which is suitable for photomechanical processes. More precisely, the present invention relates to a photothermographic material for photomechanical processes that can provide images showing low fog, high Dmax (maximum density) and little increase of fog during storage.

RELATED ART

[0002] A large number of photosensitive materials are known which -have a photosensitive image-forming layer on a support and form images by exposing imagewise. Among such materials, as an example of a system that contributes to environmental protection or enables simplification of image formation means, there is a technique of forming an image by heat development.

[0003] In recent years, reduction of amount of waste processing solutions is strongly desired in the field of photomechanical processes from the standpoints of environmental protection and space savings. Therefore, techniques relating to photothermographic materials for use in photomechanical processes are required to be developed, which enables efficient exposure by a laser scanner or a laser image setter and formation of a clear black image having high resolution and sharpness. Such photothermographic materials can provide users with a simpler and non-polluting heat development processing system that eliminates the use of solution-type processing chemicals.

[0004] Methods for forming images by heat development are described in, for example, U.S. Pat. Nos. 3,152,904, 3,457,075 and D. Klosterboer, Imaging Processes and Materials, “Thermally Processed Silver Systems A”, 8th ed., Chapter 9, page 279, compiled by J. Sturge, V. Walworth and A. Shepp, Neblette (1989). Such a photothermographic material contains a reducible non-photosensitive silver source (e.g., silver salt of an organic acid), a photocatalyst (e.g., silver halide) in a catalytically active amount, and a reducing agent for silver, which are usually dispersed in an organic binder matrix. Such a photosensitive material is stable at an ambient temperature, but when the material is heated at a high temperature (e.g., 80° C. or higher) after light exposure, silver is produced through an oxidation-reduction reaction between the reducible silver source (which functions as an oxidizing agent) and the reducing agent. The oxidation-reduction reaction is accelerated by catalytic action of a latent image generated upon exposure. The silver produced by the reaction of the reducible silver salt in the exposed region shows black color and this presents a contrast to the non-exposed region to form an image.

[0005] For use of photomechanical process films in the fields of newspaper printing, commercial printing and so forth, there have generally been desired systems that can provide stable images at any time. However, photothermographic materials showing such high-contrast photographic property as mentioned above, which is required for films for photomechanical processes, suffer from a problem that they are more likely to cause fog and, in particular, suffer from more significant increase of fog during storage compared with conventional films that are treated with chemicals.

[0006] Therefore, it has been desired to provide a photothermographic material that shows low fog, high Dmax (maximum density) and little increase of fog during storage.

SUMMARY OF THE INVENTION

[0007] In view of the aforementioned problems of the conventional techniques, an object of the present invention is to provide a photothermographic material especially for photomechanical processes, in particular, for scanners and image setters, which shows high sensitivity, low fog, high Dmax (maximum density) and little increase of fog during storage.

[0008] The inventor of the present invention conducted various researches, and as a result, he found that if the ratio of twin crystal grains of photosensitive silver halide was 1.0% or less with respect to the total grain number of the photosensitive silver halide, the aforementioned object could be achieved, and thus accomplished the present invention.

[0009] That is, the present invention provides a photothermographic material containing a photosensitive silver halide, a non-photosensitive silver salt of an organic acid, a reducing agent for silver ions and a binder on one surface of a support, wherein a ratio of twin crystal grains of the photosensitive silver halide is 1.0% or less with respect to the total grain number of the photosensitive silver halide.

[0010] The photosensitive silver halide grains used for the present invention preferably have a monodispersion degree of 30% or less for grain size distribution, and the photosensitive silver halide is preferably contained as an emulsion containing low molecular weight gelatin having a molecular weight of 500-60,000.

[0011] Furthermore, the photothermographic material of the present invention preferably contains a high contrast agent.

[0012] The photothermographic material of the present invention can be exposed within 10−6 second or less. Further, the photothermographic material of the present invention can be exposed with a multi-beam light exposure apparatus provided with two or more laser heads. Furthermore, the photothermographic material of the present invention can be subjected to a heat development treatment at a line speed of 140 cm/minute or more.

[0013] According to the present invention, there is provided a photothermographic material that shows high sensitivity, low fog and little increase of fog during storage, that is, photographic properties suitable for use in photomechanical processes.

[0014] Furthermore, according to the present invention, the aforementioned favorable photographic properties can be obtained even when the photothermographic material is exposed within 10−6 second or less, exposed with a multi-beam light exposure apparatus provided with two or more laser heads or subjected to a heat development treatment at a line speed of 140 cm/minute or more.

BRIEF DESCRIPTION OF THE DRAWING

[0015]
FIG. 1 is a side view of an exemplary heat developing apparatus used for heat development of the photothermographic material of the present invention. In the figure, there are shown a photothermographic material 10, carrying-in roller pairs 11, taking-out roller pairs 12, rollers 13, a flat surface 14, heaters 15, and guide panels 16. The apparatus consists of a preheating section A, a heat development section B, and a gradual cooling section C.

DETAILED DESCRIPTION OF THE INVENTION

[0016] The photothermographic material of the present invention will be explained in detail hereafter. In the following description, ranges indicated with “-” mean ranges including the numerical values before and after “-” as the minimum and maximum values.

[0017] The photothermographic material of the present invention is a photothermographic material containing a photosensitive silver halide, a non-photosensitive silver salt of an organic acid, a reducing agent for silver ions and a binder on one surface of a support, wherein a ratio of twin crystal grains of the photosensitive silver halide is 1.0% or less with respect to the total grain number of the photosensitive silver halide.

[0018] First, the silver halide grains, which constitute the characteristic of the present invention, will be explained.

[0019] It is preferred that grains of the photosensitive silver halide used for the photothermographic material of the present invention substantially do not to have twin planes. The expression of “substantially do not to have twin planes” means that the ratio of grains having twin planes should be 1.0% or less, preferably 0.5% or less, more preferably 0.2% or less, further preferably 0.1% or less. Most preferably, twin crystal grains should exist in an undetectable amount. As for the details of twin crystal grain structure, one can refer to the descriptions of “Die Grundlagen der Photographischen Prozesse mit Silber-halogeniden”, compiled by H. Frieser et al., Chapter 3, Akademische verlagsgesellschaft, Trankfurt am Main (1968).

[0020] The ratio of twin crystal grain number (grain number ratio) can be obtained by maintaining a grain emulsion at a temperature of 40° C. or lower, preferably 35° C. or lower, to allow grains to grow until they have a definite grain shape under a highly supersaturated condition without generation of new nuclei, and observing a transmission electron microscopy image (TEM image) of replica of the grains. As for the details of this technique, one can referred to the descriptions of Japanese Patent Laid-open Publication (Kokai, hereinafter referred to as JP-A) No. 2-146033.

[0021] In order to form silver halide fine grains having a small grain size, in general, aqueous solutions of a silver salt and an X− salt can be added within a short period of time under a condition of solubility of AgX as low as possible (a region of pAg showing the lowest solubility at a temperature as low as possible in the absence of a solvent for AgX is selected from an AgX solubility curve) and a stirring efficiency as better as possible. However, addition of the aqueous solutions of silver salt and X salt at a low temperature within a short period of time leads to increase of formation probability of the aforementioned twin crystal grains. However, in order to form AgX fine grains, use of such conditions is unavoidable. Therefore, other supersaturation factors at the time of nucleation are controlled for formation of less twin planes. Specifically, one or more of the following techniques can be used, and the following factors can be controlled so that the characteristic of the formed grains should satisfy the above definition.

[0022] 1) Use of High Gelatin Concentration

[0023] As the gelatin concentration in the reaction solution becomes higher, the formation probability of twin planes decreases. However, in case of usual gelatin for photographic use, an unduly high gelatin concentration invites a high viscosity or gellation of the reaction solution, in particular, at a low temperature, and thus the stirring efficiency is degraded. Therefore, a preferred gelatin concentration in the reaction solution at the time of the start of the reaction is 1-10 weight %, more preferably 3-8 weight %.

[0024] 2) Use of Low Molecular Weight Gelatin

[0025] If the molecular weight of gelatin used is changed in a solution of a constant weight % concentration thereof, the formation probability of twin planes becomes lowest in the molecular weight range of 1-60,000. Therefore, gelatin having a molecular weight of 500-60,000, more preferably 10,000-30,000, is used. Further, such low molecular weight gelatin is preferred from the standpoint that it does not show high viscosity or gellation even at a low temperature. For example, a 10 weight % solution of gelatin having a molecular weight of 10,000 does not gel even at 0° C. Therefore, even when a high gelatin concentration is used at a low temperature, no gellation occurs, and low formation probability of twin planes is obtained. Thus, such gelatin is particularly preferred. The gelatin concentration is preferably in the range of 1-15 weight %, more preferably 3-12 weight %.

[0026] 3) Addition of Gelatin to at Least One of Aqueous Solutions of Silver Salt and X− Salt Before Mixing

[0027] This is employed because the gelatin concentration is usually lowered around the site where the aforementioned solutions are added and it increases the formation frequency of twin planes. Since the supersaturation degree becomes particularly high around addition nozzles, decrease of the gelatin concentration around them is not preferred. More preferably, gelatin is added to both of the aqueous solutions of silver salt and X− salt. In this case, in order to prevent white turbidity of the silver salt solution due to formation of silver hydroxide or silver oxide, an acid such as HNO3 can be added to adjust the pH to be 5 or less. As for gelatin having an average molecular weight of about 100,000, which is usually used in the field of photography, the gelatin concentration is preferably 1.6 weight % or less, morepreferably 1.6-0.2 weight %, in view of prevention of gellation of its aqueous solution. On the other hand, when low molecular weight gelatin (average molecular weights: 1000-60,000) is used, it is preferably used in an amount of 10 weight % or less, more preferably 10-0.2 weight %, since it does not cause gellation.

[0028] 4) Formation of Fine Grains at Around Isoionic Points of Ag+ and X− Concentrations

[0029] If concentrations of excess Br−, I− and Cl− in the reaction solution are reduced during fine grain formation, the twin plane formation probability is lowered. When the nucleation is attained under an X− excess condition, the order of contribution degrees to the twin plane formation of these ions is represented as I−>Br−>Cl−, on the basis of comparison at the same molar concentrations. Therefore, it is particularly important to decrease the concentrations of excess I− and Br−. Conversely, if the nucleation is attained under an Ag+ excess condition, decrease of excess Ag+ concentration lowers the formation probability of twin planes. That is, less excess amount of Ag+ or X− leads to lower formation probability of twin planes. The excess X− concentration or excess Ag+ concentration at the time of silver halide fine grain formation is preferably 0-10−2.1 M/L, more preferably 0-10−2.5 M/L. This condition corresponds to the aforementioned low solubility region of AgX solubility curve, and it is a preferred region also as a fine grain formation condition.

[0030] 5) Use of Lower pH

[0031] When gelatin is used as a dispersion medium, a lower pH of the reaction solution provides lower twin plane formation probability. This dependency is more significant in an AgCl system rather than AgBr system. pH is preferably in the range of 5 or less, more preferably 4-1.8. However, there is also a case where the relationship of pH is in inverse relationship. Therefore, it is preferable to experimentally obtain an optimum pH for each case in practical use.

[0032] 6) Use of Higher Concentrations of Salts not Involved in Formation of Photosensitive Silver Halide

[0033] Higher concentrations of unrelated salts such as KNO3 and NaNO3 in the reaction solution provide lower twin plane formation probability. Concentrations of such salts are preferably in the range of 0-1 M/L, more nearly preferably 1×10−2 to 1 M/L.

[0034] 7) Use of Lower I− Content in X− Salt Solution Added Upon Nucleation (This Technique Also Relates to the Aforementioned Item 4))

[0035] A higher content of I− in the X− salt solution added upon nucleation during the silver halide fine grain formation provides higher twin plane formation probability. Therefore, the I− content is preferably made as low as possible.

[0036] 8) Addition of Silver Salt and X− Salt by Accelerated Addition Method

[0037] This technique is explained as follows. In general, the aqueous solutions of silver salt and X− salt are added by the simultaneous addition method at constant rates in a short period of time in many cases. However, since the supersaturation degrees become highest during an early stage of the addition and thus twin planes are likely to be formed, the addition rates are reduced to an order of 1/n, where n is preferably 1.2-30, more preferably 2-30, during an early stage (at least 10 seconds from the start of the addition). This reduces the generation probability of twin planes, but also reduces the number of produced nuclei. This leads to increase of grain size ultimately obtained when silver is added in the same amount. Therefore, the addition is subsequently performed at an m-time higher addition rates (specifically, 1.2-30 times, preferably 2-30 times, of the addition rate that causes generation of new nuclei) to increase the number of grains. The aforementioned n, m and the number of steps (this acceleration step number is an integer of 1-30) are selected so that the number of formed grains should exceed the number of formed grains obtained by a conventional method on the basis of use of the same molar number of silver salt as an aqueous solution. Further, growth of the initially formed nuclei is suppressed as much as possible by selecting a low temperature (45° C. or lower) and low solubility conditions.

[0038] As for these relationships between the nucleation conditions and twin plane formation frequency, one can refer to the descriptions of JP-A-63-92942, JP-A-2-838 and JP-A-2-146033.

[0039] Further, as for a mixing apparatus that can be preferably used to prepare the non-twin crystal silver halide fine grains (silver halide fine grains containing an extremely small amount of twin crystal grains) used for the present invention, one can refer to the descriptions of JP-A-9-197587.

[0040] The photosensitive silver halide used for the present invention is not particularly limited as for the halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide and so forth may be used. As for the preparation of grains of the photosensitive silver halide emulsion, the grains can be prepared by the method described in JP-A-11-119374, paragraphs 0127-0224. However, the method is not particularly limited to this method.

[0041] Examples of the form of silver halide grains include a cubic form, octahedral form, tetradecahedral form, potato-like form and so forth. In particular, cubic grains are preferred for the present invention. As for the characteristics of the grain form such as surface index of the grains, they may be similar to those described in JP-A-11-119374, paragraph 0225. Further, the halogen composition may have a uniform distribution in the grains, or the composition may change stepwise or continuously in the grains. Silver halide grains having a core/shell structure may also be preferably used. Core/shell grains having preferably a double to quintuple structure, more preferably a double to quadruple structure may be used. A technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains may also be preferably used.

[0042] The grain size of the silver halide grains of the photosensitive silver halide used in the present invention is not particularly limited. However, a smaller grain size is more preferred in order to suppress white turbidity after the image formation, and specifically, the grain size is preferably 0.12 um or less, more preferably 0.01-0.1 μm.

[0043] As for the grain size distribution of the silver halide grains that can be used in the present invention, the grains show monodispersion degree of 30% or less, preferably 1-20%, more preferably 5-15%. The monodispersion degree used herein is defined as a percentage (%) of a value obtained by dividing standard deviation of grain size with average grain size (variation coefficient). The grain size of the silver halide grains is represented as a ridge length for cubic grains, or a diameter as circle of projected area for the other grains (octahedral grains, tetradecahedral grains and so forth) for convenience.

[0044] The photosensitive silver halide grains that can be used in the present invention preferably contain a metal of Group VII or Group VIII in the periodic table of elements or a complex of such a metal. The metal or the center metal of the complex of a metal of Group VII or Group VIII of the periodic table is preferably rhodium, rhenium, ruthenium, osmium or iridium. Particularly preferred metal complexes are (NH4)3Rh(H2O)Cl5, K2Ru (NO)Cl5, K3IrCl6 and K4Fe(CN)6. The metal complexes may be used each alone, or two or more complexes of the same or different metals may also be used in combination. The content is preferably from 1×10−9 to 1×10−3 mole, more preferably 1×10−8 to 1×10−4 mole, per mole of silver. As for specific structures of metal complexes, metal complexes of the structures described in JP-A-7-225449 and so forth can be used. Types and addition methods of these heavy metals and complexes thereof are described in JP-A-11-119374, paragraphs 0227-0240.

[0045] The photosensitive silver halide grains may be desalted by washing methods with water known in the art, such as the noodle washing and flocculation. However, the grain may not be desalted in the present invention.

[0046] The photosensitive silver halide emulsion used for the present invention is preferably sensitized by chemical sensitization. For the chemical sensitization, the methods described in JP-A-11-119374, paragraphs 0242-0250 and U.S. Pat. No. 4,810,626 are preferably used.

[0047] Silver halide emulsions used in the present invention may be added with thiosulfonic acid compounds by the method described in EP-A-293917A.

[0048] As gelatin contained in the photosensitive silver halide emulsions used in the present invention, low molecular weight gelatin is preferably used in order to maintain good dispersion state of the silver halide emulsion in a coating solution containing a silver salt of an organic acid. The low molecular weight gelatin has a molecular weight of preferably 500-60,000, more preferably 1,000-40,000. Such low molecular weight gelatin may be added during the formation of grains or dispersion operation after the desalting treatment.

[0049] While the concentration of dispersion medium may be 0.05-20 weight %, it is preferably in the range of 5-15 weight % in view of handling. As for type of gelatin, alkali-treated gelatin is usually used. Besides that, however, modified gelatin such as acid-treated gelatin and phthalated gelatin can also be used.

[0050] As for the photosensitive silver halide emulsion used in the photosensitive material of the present invention, one kind of photosensitive silver halide emulsion may be used or two or more different emulsions (for example, those having different average grain sizes, different halogen compositions, different crystal habits or those subjected to chemical sensitization under different conditions) may be used in combination.

[0051] The amount of the photosensitive silver halide per mole of the silver salt of an organic acid is preferably from 0.01-0.5 mole, more preferably from 0.02-0.3 mole, still more preferably from 0.03-0.25 mole. Methods and conditions for mixing photosensitive silver halide and silver salt of an organic acid, which are prepared separately, are not particularly limited so long as the effect of the present invention can be attained satisfactorily. Examples thereof include, for example, a method of mixing silver halide grains and silver salt of an organic acid after completion of respective preparations by using a high-speed stirring machine, ball mill, sand mill, colloid mill, vibrating mill, homogenizer or the like, or a method of preparing a silver salt of an organic acid with mixing a photosensitive silver halide obtained separately at any time during the preparation of the silver salt of an organic acid. For the mixing of them, mixing of two or more kinds of aqueous dispersions of the silver salt of an organic acid and two or more kinds of aqueous dispersions of the photosensitive silver salt is preferably used for controlling photographic properties.

[0052] In the photothermographic material of the present invention, it is preferable to use a high contrast agent.

[0053] Specific examples of high contrast agents that can be used in the present invention will be mentioned below:

[0054] all of the hydrazine derivatives represented by the formula (H) mentioned in JP-A-2000-284399 (specifically, the hydrazine derivatives mentioned in Tables 1-4 of the same), the hydrazine derivatives described in JP-A-10-10672, JP-A-10-161270, JP-A-10-62898, JP-A-9-304870, JP-A-9-304872, JP-A-9-304871, JP-A-10-31282, U.S. Pat. No. 5,496,695 and EP-A-741,320: and the substituted alkene derivatives, substituted isoxazole derivatives and particular acetal compounds represented by the formulas (1) to (3) mentioned in JP-A-2000-284399, and the cyclic compounds represented by the formula (A) or (B) mentioned in the same, specifically Compounds 1-72 mentioned in Chemical Formulas 8-12 of the same.

[0055] As a compound used as a high contrast agent in the photothermographic material of the present invention, more preferred are the compounds represented by the formula (1) mentioned in JP-A-11-149136. Specific examples of the compounds represented by the formula (1) are shown below. However, compounds used in the present invention as a high contrast agent are not limited to the following compounds. In the following structural formulas, “Am” represents amyl group.

YXCH3PhOHOCH3Si(CH3)3

1a1b1c1d1e

2a2b2c2d2e

3a3b3c3d3e

4a4b4c4d4e

5a5b5c5d5e

6a6b6c6d6e

7a7b7c7d7e

8a8b8c8d8e

9a9b9c9d9e

YXCH3OHPhHCH2CO2H

10a10b10c10d10e

11a11b11c11d11e(C2H5)2N—12a12b12c12d12e

13a13b13c13d13e

14a14b14c14d14e

15a15b15c15d15e

16a16b16c16d16e

17a17b17c17d17e

18a18b18c18d18e

YXHCH3PhOCH3N(CH3)2

19a19b19c19d19e

20a20b20c20d20e

21a21b21c21d21e

22a22b22c22d22e

23a23b23c23d23e

24a24b24c24d24e

25a25b25c25d25e

26a26b26c26d26e

27a27b27c27d27e

YXCH3PhOHSi(CH3)3OCH2

28a28b28c28d28e

29a29b29c29d29e

30a30b30c30d30e

31a31b31c31d31e

32a32b32c32d32e

33a33b33c33d33e

34a34b34c34d34e

35a35b35c35d35e

36a36b36c36d36e

100

101

102

103

100

104

101

105

102

106

103

[0056] Further, the formic acid precursors described in Japanese Patent Application No. 2000-313207 can also be preferably used. Specific examples of those compounds are mentioned below.

107

108

[0057] Furthermore, the compounds represented by the formula (2) (3) or (4) mentioned in JP-A-2000-284405 can also be preferably used. Specific examples of those compounds are mentioned below.

109

110

111

112

113

114

115

116

117

118

[0058] The compounds used as a high contrast agent in the present invention may be used after being dissolved in water or an appropriate organic solvent such as alcohols (e.g., methanol, ethanol, propanol, fluorinated alcohol), ketones (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide or methyl cellosolve.

[0059] The compounds may also be used as an emulsified dispersion mechanically prepared according to an already well known emulsification dispersion method by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, ethyl acetate or cyclohexanone as an auxiliary solvent for dissolution. Alternatively, the compounds may be used after dispersion of a powder of the compounds in a suitable solvent such as water by using a ball mill, a colloid mill or the like, or by means of ultrasonic wave according to a known method for solid dispersion.

[0060] The compounds used as a high contrast agent in the present invention may be used each alone one in a combination of two or more of them. The compounds used as a high contrast agent in the present invention may be added to any layers on the image-forming layer side of the support. However, the compounds are preferably added to the image-forming layer or a layer adjacent thereto.

[0061] The amount of the compounds used as a high contrast agent in the present invention is preferably from 1×10−6 to 1 mole, more preferably from 1×10−5 to 5×10−1 mole, most preferably from 2×10−5 to 2×10−1 mole, per mole of silver.

[0062] In the present invention, a contrast accelerator may be used in combination with the above-described compounds for the formation of an ultrahigh contrast image. For example, amine compounds described in U.S. Pat. No. 5,545,505, specifically, AM-1 to AM-5; hydroxamic acids described in U.S. Pat. No. 5,545,507, specifically, HA-1 to HA-11; acrylonitriles described in U.S. Pat. No. 5,545,507, specifically, CN-1 to CN-13; hydrazine compounds described in U.S. Pat. No. 5,558,983, specifically, CA-1 to CA-6; and onium salts described in JP-A-9-297368, specifically, A-1 to A-42, B-1 to B-27 and C-1 to C-14 and so forth may be used.

[0063] The non-photosensitive silver salt of organic acid, which is one of the basic components of the photothermographic material of the present invention, will be explained hereafter.

[0064] The silver salt of an organic acid that can be used for the present invention is a silver salt relatively stable against light, but forms a silver image when it is heated at 80° C. or higher in the presence of an exposed photocatalyst (e.g., a latent image of photosensitive silver halide) and a reducing agent. The silver salt of an organic acid may be any organic substance containing a source of reducible silver ions. Silver salts of an organic acid, in particular, silver salts of a long chained aliphatic carboxylic acid having 10-30 carbon atoms, preferably from 15-28 carbon atoms, are preferred. Complexes of organic or inorganic acid silver salts of which ligands have a complex stability constant in the range of 4.0-10.0 are also preferred. The silver supplying substance can preferably constitute about 5-70 weight % of the image-forming layer. Preferred examples of the silver salts of an organic acid include silver salts of organic compounds having carboxyl group. Specifically, the silver salts of an organic acid may be silver salts of an aliphatic carboxylic acid and silver salts of an aromatic carboxylic acid, but not limited to these. Preferred examples of the silver salts of an aliphatic carboxylic acid include silver behenate, silver arachidinate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate, silver camphorate, mixtures thereof and so forth.

[0065] In the present invention, there is preferably used silver salt of an organic acid having a silver behenate content of 75 mole % or more, more preferably silver salt of an organic acid having a silver behenate content of 85 mole % or more, among the aforementioned silver salts of an organic acid and mixtures of silver salts of an organic acid. The silver behenate content used herein means a molar percent of silver behenate with respect to silver salt of an organic acid to be used. As silver salts of an organic acid other than silver behenate contained in the silver salts of organic acid used for the present invention, the silver salts of an organic acid exemplified above can preferably be used.

[0066] Silver salts of an organic acid that can be preferably used for the present invention can be prepared by allowing a solution or suspension of an alkali metal salt (e.g., Na salts, K salts, Li salts) of the aforementioned organic acids to react with silver nitrate. As the preparation method, the method described in JP-A-2000-292882, paragraphs 0019-0021 can be used.

[0067] In the present invention, a method of preparing a silver salt of an organic acid by adding an aqueous solution of silver nitrate and a solution of alkali metal salt of an organic acid to a sealable means for mixing liquids can preferably be used. Specifically, the method described in JP-A-2000-33907 can be used.

[0068] In the present invention, a dispersing agent soluble in water can be added to the aqueous solution of silver nitrate and the solution of alkali metal salt of an organic acid or reaction mixture during the preparation of the silver salt of an organic acid. Type and amount of the dispersing agent used in this case are specifically mentioned in JP-A-2000-305214, paragraph 0052.

[0069] The silver salt of an organic acid for use in the present invention is preferably prepared in the presence of a tertiary alcohol. The tertiary alcohol preferably has a total carbon number of 15 or less, more preferably 10 or less. Examples of preferred tertiary alcohols include tert-butanol. However, tertiary alcohol that can be used for the present invention is not limited to it.

[0070] The tertiary alcohol used for the present invention may be added in any timing during the preparation of the organic acid silver salt, but the tertiary alcohol is preferably used by adding at the time of preparation of the organic acid alkali metal salt to dissolve the alkali metal salt of an organic acid. The tertiary alcohol for use in the present invention may be added in any amount of 0.01-10 in terms of the weight ratio to water used as a solvent for the preparation of the silver salt of an organic acid, but preferably added in an amount of 0.03-1 in terms of weight ratio to water.

[0071] Although shape and size of the organic acid silver salt are not particularly limited, those mentioned in JP-A-2000-292882, paragraph 0024 can be preferably used. The shape of the organic acid silver salt can be determined from a transmission electron microscope image of organic silver salt dispersion. An example of the method for determining monodispesibility is a method comprising obtaining the standard deviation of a volume weight average diameter of the organic acid silver salt. The percentage of a value obtained by dividing the standard deviation by the volume weight average diameter (variation coefficient) is preferably 80% or less, more preferably 50% or less, particularly preferably 30% or less. As a measurement method, for example, the grain size can be determined by irradiating organic acid silver salt dispersed in a liquid with a laser ray and determining an autocorrelation function for change of the fluctuation of the scattered light with time (volume weight average diameter). The average grain size determined by this method is preferably from 0.05-10.0 μm, more preferably 0.1-5.0 μm, further preferably 0.1-2.0 μm, as in solid fine grain dispersion.

[0072] The silver salt of an organic acid used in the present invention is preferably desalted. The desalting method is not particularly limited and any known methods may be used. Known filtration methods such as centrifugal filtration, suction filtration, ultrafiltration and flocculation washing by coagulation may be preferably used. As the method of ultrafiltration, the method described in JP-A-2000-305214 can be used.

[0073] For obtaining an organic acid silver salt solid dispersion having a high S/N ratio and a small grain size and being free from coagulation, there is preferably used a dispersion method comprising steps of converting an aqueous dispersion that contains a silver salt of an organic acid as an image-forming medium and contains substantially no photosensitive silver salt into a high-speed flow dispersion, and then releasing the pressure. As such a dispersion method, the method mentioned in JP-A-2000-292882, paragraphs 0027-0038 can be used.

[0074] The grain size distribution in the organic acid silver salt fine grain solid dispersion preferably corresponds to monodispersion. Specifically, the percentage (variation coefficient) of the value obtained by dividing the standard deviation of the volume weight average diameter with the volume weight average diameter is preferably 80% or less, more preferably 50% or less, particularly preferably 30% or less.

[0075] The organic acid silver salt fine grain solid dispersion used for the present invention consists at least of a silver salt of an organic acid and water. While the ratio of the silver salt of an organic acid and water is not particularly limited, the ratio of the silver salt of an organic acid is preferably in the range of 5-50 weight %, particularly preferably 10-30 weight %, with respect to the total weight. While it is preferred that the aforementioned dispersing agent should be used, it is preferably used in a minimum amount within a range suitable for minimizing the grain size, and it is preferably used in an amount of 0.5-30 weight %, particularly preferably 1-15 weight %, with respect to the silver salt of an organic acid.

[0076] The silver salt of an organic acid for use in the present invention may be used in any desired amount. However, it is preferably used in an amount of 0.1-5 g/m2, more preferably 1-3 g/m2, in terms of silver.

[0077] In the present invention, metal ions selected from Ca, Mg, Zn and Ag are preferably added to the non-photosensitive silver salt of an organic acid. The metal ions selected from Ca, Mg, Zn and Ag are preferably added to the non-photosensitive p silver salt of an organic acid in the form of a water-soluble metal salt, not a halide compound. Specifically, they are preferably added in the form of nitrate or sulfate. Addition of halide is not preferred, since it degrades image storability, i.e., so-called printing-out property, of the photosensitive material against light (indoor light, sun light etc.) after the development. Therefore, in the present invention, it is preferable to add the ions in the form of water-soluble metal salts, which are not halide compounds.

[0078] The metal ions selected from Ca, Mg, Zn and Ag, which are preferably used in the present invention, may be added any time after the formation of non-photosensitive organic acid silver salt grains and immediately before the coating operation, for example, immediately after the formation of grains, before dispersion, after dispersion, before and after the formation of coating solution and so forth. They are preferably added after dispersion, or before or after the formation of coating solution.

[0079] In the present invention, the metal ions selected from Ca, Mg, Zn and Ag are preferably added in an amount of 10−3 to 10−1 mole, particularly 5×10−3 to 5×10−2 mole, per one mole of non-photosensitive silver salt of an organic acid.

[0080] The reducing agent for silver ions, which is one of the basic components of the photothermographic material of the present invention, will be explained hereafter.

[0081] The photothermographic material of the present invention contains a reducing agent for silver ions (silver salt of an organic acid). The reducing agent for the silver salt of an organic acid may be any substance that reduces silver ions to metal silver, preferably such an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but a hindered phenol reducing agent is preferred. The reducing agent is preferably contained in an amount of from 5-50 mole %, more preferably from 10-40 mole %, per mole of silver on the side having the image-forming layer. The reducing agent may be added to any layer on the side having an image-forming layer of the support. In the case of adding the reducing agent to a layer other than the image-forming layer, the reducing agent is preferably used in a slightly large amount of from 10-50 mole % per mole of silver. The reducing agent may also be a so-called precursor that is derived to effectively function only at the time of development.

[0082] For photothermographic materials using a silver salt of an organic acid, reducing agents of a wide range can be used. There can be used, for example, the reducing agents disclosed in JP-A-46-6074, JP-A-47-1238, JP-A-47-33621, JP-A-49-46427, JP-A-49-115540, JP-A-50-14334, JP-A-50-36110, JP-A-50-147711, JP-A-51-32632, JP-A-51-32324, JP-A-51-51933, JP-A-52-84727, JP-A-55-108654, JP-A-56-146133, JP-A-57-82828, JP-A-57-82829, JP-A-6-3793, U.S. Pat. Nos. 3,679,426, 3,751,252, 3,751,255, 3,761,270, 3,782,949, 3,839,048, 3,928,686 and 5,464,738, German Patent No. 2,321,328, EP-A-692732A and so forth. Examples thereof include amidoximes such as phenylamidoxime, 2-thienyl-amidoxime and p-phenoxyphenylamidoxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; combinations of an aliphatic carboxylic acid arylhydrazide with ascorbic acid such as a combination of 2,2-bis(hydroxymethyl)propionyl-β-phenyl-hydrazine with ascorbic acid; combinations of polyhydroxybenzene with hydroxylamine, reductone and/or hydrazine such as a combination of hydroquinone with bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine; hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-anilinehydroxamic acid; combinations of an azine with a sulfonamidophenol such as a combination of phenothiazine with 2,6-dichloro-4-benzenesulfonamidophenol; α-cyanophenylacetic acid derivatives such as ethyl-α-cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate; bis-β-naphthols such as 2,2′-dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl and bis(2-hydroxy-1-naphthyl)-methane; combinations of a bis-p-naphthol with a 1,3-dihydroxybenzene derivative (e.g., 2,4-dihydroxybenzophenone, 2′,4′-dihydroxyacetophenone); 5-pyrazolones such as 3-methyl-1-phenyl-5-pyrazolone; reductones such as dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidonehexose reductone; sulfonamidophenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and so forth; chromans such as 2,2-dimethyl-7-t-butyl-6-hydroxychroman; 1,4-dihydropyridines such as 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine; bisphenols such as bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-ethylidene-bis(2-tert-butyl-6-methylphenol), 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; ascorbic acid derivatives such as 1-ascorbyl palmitate and ascorbyl stearate; aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and a certain kind of indane-1,3-diones; chromanols such as tocopherol and so forth. Particularly preferred reducing agents are bisphenols and chromanols.

[0083] The reducing agent used in the present invention may be added in any form of an aqueous solution, solution in an organic solvent, powder, solid microparticle dispersion, emulsion dispersion or the like. The solid microparticle dispersion is performed by using a known pulverizing means (e.g., ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill). At the time of solid microparticle dispersion, a dispersion aid may also be used.

[0084] The binder, which is one of the basic components of the photothermographic material of the present invention, will be explained hereafter.

[0085] Examples of the binder used in the present invention include natural polymers, synthetic resins, synthetic homopolymers and copolymers and other film-forming media. Specific examples thereof include, for example, gelatin, gum arabic, poly(vinyl alcohol), hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, poly(vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylate), poly(vinyl chloride), poly(methacrylic acid), copoly(styrene-maleic anhydride), copoly(styrene-acrylonitrile), copoly(styrene-butadiene), poly(vinyl acetal) (e.g., poly(vinyl formal), poly(vinylbutyral)), poly(ester), poly(urethane), phenoxyresin, poly(vinylidene chloride), poly(epoxide), poly(carbonate), poly(vinyl acetate), cellulose ester, poly(amide) and so forth.

[0086] Although the binder may be hydrophilic or hydrophobic, it is preferable to use a hydrophobic transparent binder in order to reduce fog after heat development. Preferred binders are polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and so forth. Among these, polyvinyl butyral, cellulose acetate and cellulose acetate butyrate are particularly preferably used.

[0087] Further, in order to protect a surface or prevent scratches, the photothermographic material may have a protective layer outside the image-forming layer. Type of the binder used for the protective layer may be the same as or different from that of the binder used for the image-forming layer. Usually used is a polymer having a softening point higher than that of the binder polymer constituting the image-forming layer in order to prevent scratches, deformation of the layer and so forth, and cellulose acetate, cellulose acetate butyrate and so forth are appropriate for this purpose.

[0088] When the binder used in the present invention is coated by using a solvent (dispersion medium) containing water as a main component, the polymer latex described below is preferably used.

[0089] Among image-forming layers containing a photosensitive silver halide in the photothermographic material of the present invention, at least one layer is preferably an image-forming layer utilizing polymer latex to be explained below in an amount of 50 weight % or more with respect to the total amount of binder. The polymer latex may be used not only in the image-forming layer, but also in the protective layer, back layer or the like. When the photothermographic material of the present invention is used for, in particular, printing use in which dimensional change causes problems, the polymer latex is preferably used also in a protective layer and a back layer. The term “polymer latex” used herein means a dispersion comprising hydrophobic water-insoluble polymer dispersed in a water-soluble dispersion medium as fine particles. The dispersed state may be one in which polymer is emulsified in a dispersion medium, one in which polymer underwent emulsion polymerization, micelle dispersion, one in which polymer molecules having a hydrophilic portion themselves are dispersed in molecular state or the like. The polymer latex used in the present invention is described in “Gosei Jushi Emulsion (Synthetic Resin Emulsion)”, compiled by Taira Okuda and Hiroshi Inagaki, issued by Kobunshi Kanko Kai (1978); “Gosei Latex no Oyo (Application of Synthetic Latex)”, compiled by Takaaki Sugimura, Yasuo Kataoka, Souichi Suzuki and Keishi Kasahara, issued by Kobunshi Kanko Kai (1993); Soichi Muroi, “Gosei Latex no Kagaku (Chemistry of Synthetic Latex)”, Kobunshi Kanko Kai (1970) and so forth. The dispersed particles preferably have an average particle size of about 1-50000 nm, more preferably about 5-1000 nm. The particle size distribution of the dispersed particles is not particularly limited, and the particles may have either wide particle size distribution or monodispersed particle size distribution.

[0090] The polymer latex used in the present invention may be latex of the so-called core/shell type other than ordinary polymer latex having a uniform structure. In this case, use of different glass transition temperatures of core and shell may be preferred.

[0091] Preferred range of the glass transition temperature (Tg) of the polymer latex preferably used as the binder in the present invention varies for the protective layer, back layer and image-forming layer. As for the image-forming layer, the glass transition temperature is preferably −30-40° C. for accelerating diffusion of photographic elements during the heat development. Polymer latex used for the protective layer or back layer preferably has a glass transition temperature of 25-70° C., because these layers are brought into contact with various apparatuses.

[0092] The polymer latex used in the present invention preferably shows a minimum film forming temperature (MFT) of about −30-90° C., more preferably about 0-70° C. A film-forming aid may be added in order to control the minimum film forming temperature. The film-forming aid is also referred to as a plasticizer, and consists of an organic compound (usually an organic solvent) that lowers the minimum film forming temperature of the polymer latex. It is explained in, for example, the aforementioned Soichi Muroi, “Gosei Latex no Kagaku (Chemistry of Synthetic Latex)”, Kobunshi Kanko Kai (1970).

[0093] Examples of polymer species used for the polymer latex used in the present invention include acrylic resin, polyvinyl acetate resin, polyester resin, polyurethane resin, rubber resin, polyvinyl chloride resin, polyvinylidene chloride resin and polyolefin resin, copolymers of monomers constituting these resins and so forth. The polymers may be linear, branched or crosslinked. They may be so-called homopolymers in which a single kind of monomers are polymerized, or copolymers in which two or more different kinds of monomers are polymerized. The copolymers may be random copolymers or block copolymers. The polymers may have a number average molecular weight of about 5,000 to 1,000,000, preferably from about 10,000 to 100,000. Polymers having a too small molecular weight may unfavorably suffer from insufficient mechanical strength of the image-forming layer, and those having a too large molecular weight may unfavorably suffer from bad film forming property.

[0094] Specific examples of the polymer latex used as the binder of the image-forming layer of the photothermographic material of the present invention include latex of methyl methacrylate/ethyl acrylate/methacrylic acid copolymer, latex of methyl methacrylate/butadiene/itaconic acid copolymer, latex of ethyl acrylate/methacrylic acid copolymer, latex of methyl methacrylate/2-ethylhexyl acrylate/styrene/acrylic acid copolymer, latex of styrene/butadiene/acrylic acid copolymer, latex of styrene/butadiene/divinylbenzene/methacrylic acid copolymer, latex of methyl methacrylate/vinyl chloride/acrylic acid copolymer, latex of vinylidene chloride/ethyl acrylate/acrylonitrile/methacrylic acid copolymer and so forth. More specifically, there can be mentioned latex of methyl methacrylate (33.5 weight %)/ethyl acrylate (50 weight %)/methacrylic acid (16.5 weight %) copolymer, latex of methyl methacrylate (47.5 weight %)/butadiene (47.5 weight %)/itaconic acid (5 weight %) copolymer, latex of ethyl acrylate (95 weight %)/methacrylic acid (5 weight %) copolymer and so forth. Such polymers are also commercially available and examples thereof include acrylic resins such as CEBIAN A-4635, 46583, 4601 (all produced by Dicel Kagaku Kogyo Co., Ltd), Nipol LX811, 814, 821, 820, 857 (all produced by Nippon Zeon Co., Ltd.), VONCORT R3340, R3360, R3370, 4280 (all produced by Dai-Nippon Ink & Chemicals, Inc.); polyester resins such as FINETEX ES650, 611, 675, 850 (all produced by Dai-Nippon Ink & Chemicals, Inc.), WD-size and WMS (both produced by Eastman Chemical); polyurethane resins such as HYDRAN AP10, 20, 30, 40 (all produced by Dai-Nippon Ink & Chemicals, Inc.); rubber resins such as LACSTAR 7310K, 3307B, 4700H, 7132C (all produced by Dai-Nippon Ink & Chemicals, Inc.), Nipol LX410, 430, 435, 438C (all produced by Nippon Zeon Co., Ltd.); polyvinyl chloride resins such as G351, G576 (both produced by Nippon Zeon Co., Ltd.); polyvinylidene chloride resins such as L502, L513 (both produced by Asahi Chemical Industry Co., Ltd.), ARON D7020, D504, D5071 (all produced by Mitsui Toatsu Co., Ltd.); and olefin resins such as CHEMIPEARL S120 and SA100 (both produced by Mitsui Petrochemical Industries, Ltd.) and so forth. These polymers may be used individually or, if desired, as a blend of two or more of them.

[0095] The image-forming layer preferably contains 50 weight % or more, more preferably 70 weight % or more, of the aforementioned polymer latex based on the total binder.

[0096] If desired, the image-forming layer may contain a hydrophilic polymer in an amount of 50 weight % or less of the total binder, such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose and hydroxypropylmethylcellulose. The amount of the hydrophilic polymer is preferably 30 weight % or less, more preferably 15 weight % or less, of the total binder in the image-forming layer.

[0097] The image-forming layer is preferably formed by coating an aqueous coating solution and then drying the coating solution. The term “aqueous” as used herein means that water content of the solvent (dispersion medium) in the coating solution is 60 weight % or more. In the coating solution, the component other than water may be a water-miscible organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide and ethyl acetate. Specific examples of the solvent composition include water/methanol=90/10, water/methanol=70/30, water/ethanol=90/10, water/isopropanol=90/10, water/dimethylformamide=95/5, water/methanol/dimethylformamide=80/15/5, and water/methanol/dimethylformamide=90/5/5 (the numerals indicate weight %).

[0098] The total amount of the binder in the image-forming layer is preferably from 0.2-30 g/m2, more preferably from 1-15 g/m2. The image-forming layer may contain a crosslinking agent for crosslinking, surfactant for improving coatability and so forth.

[0099] Further, a combination of polymer latexes having different I/O values is also preferably used as the binder of the protective layer. The I/O values are obtained by dividing an inorganicity value with an organicity value, both of which values are based on the organic conceptual diagram described in JP-A-2000-267226, paragraphs 0025-0029.

[0100] In the present invention, a plasticizer (e.g., benzyl alcohol, 2,2,4-trimethylpentanediol-1,3-monoisobutyrate etc.) described in JP-A-2000-267226, paragraphs 0021-0025 can be added as required to control the film-forming temperature. Further, a hydrophilic polymer may be added to a polymer binder, and a water-miscible organic solvent may be added to a coating solution as described in JP-A-2000-267226, paragraphs 0027-0028.

[0101] First polymer latex introduced with functional groups, and a crosslinking agent and/or second polymer latex having a functional group that can react with the first polymer latex, which are described in JP-A-2000-19678, paragraphs 0023-0041, can also be added to each layer.

[0102] The aforementioned functional groups may be carboxyl group, hydroxyl group, isocyanate group, epoxy group, N-methylol group, oxazolinyl group or so forth. The crosslinking agent is selected from epoxy compounds, isocyanate compounds, blocked isocyanate compounds, methylolated compounds, hydroxy compounds, carboxyl compounds, amino compounds, ethylene-imine compounds, aldehyde compounds, halogen compounds and so forth. Specific examples of the crosslinking agent include, as isocyanate compounds, hexamethylene isocyanate, Duranate WB40-80D, WX-1741 (Asahi Chemical Industry Co., Ltd.), Bayhydur 3100 (Sumitomo Bayer Urethane Co., Ltd.), Takenate WD725 (Takeda Chemical Industries, Ltd.), Aquanate 100, 200 (Nippon Polyurethane Industry Co., Ltd.), aqueous dispersion type polyisocyanates mentioned in JP-A-9-160172; as an amino compound, Sumitex Resin M-3 (Sumitomo Chemical Co., Ltd.); as an epoxy compound, Denacol EX-614B (Nagase Chemicals Ltd.); as a halogen compound, 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt and so forth.

[0103] The total amount of the binder for the image-forming layer is preferably in the range of 0.2-30 g/m2, more preferably 1.0-15 g/m2.

[0104] The total amount of the binder for the protective layer is preferably in the range of 1-10.0 g/m2, more preferably 2-6.0 g/m2, as an amount providing a film thickness of 3 μm or more, which is preferably used in the present invention.

[0105] In the present invention, the thickness of the protective layer is preferably 3 μm or more, more preferably 4 μm or more. While the upper limit of the thickness of the protective layer is not particularly limited, it is preferably 10 μm or less, more preferably 8 μm or less, in view of coating and drying.

[0106] The total amount of the binder for the back layer is preferably in the range of 0.01-10.0 g/m2, more preferably 0.05-5.0 g/m2.

[0107] Each of these layers may be provided as two or more layers. When the image-forming layer consists of two or more layers, it is preferred that polymer latex should be used as a binder for all of the layers. The protective layer is a layer provided on the image-forming layer, and it may consist of two or more layers. In such a case, it is preferred that polymer latex should be used for at least one of the layers, especially the outermost protective layer. Further, the back layer is a layer provided on an undercoat layer for the back surface of the support, and it may consist of two or more layers. In such a case, it is preferred that polymer latex should be used for at least one of the layers, especially the outermost back layer.

[0108] The support, which is one of the basic components of the photothermographic material of the present invention, will be explained hereafter.

[0109] For the photothermographic material of the present invention, various kinds of supports can be used. Typical supports comprise polyester such as polyethylene terephthalate and polyethylene naphthalate, cellulose nitrate, cellulose ester, polyvinylacetal, syndiotactic polystyrene, polycarbonate, paper support of which both surfaces are coated with polyethylene or the like. Among these, biaxially stretched polyester, especially polyethylene terephthalate (PET), is preferred in view of strength, dimensional stability, chemical resistance and so forth. The support preferably has a thickness of 90-180 μm as a base thickness except for the undercoat layers.

[0110] Preferably used as the support of the photothermographic material of the present invention is a polyester film, in particular polyethylene terephthalate film, subjected to a heat treatment in a temperature range of 130-185° C. in order to relax the internal distortion formed in the film during the biaxial stretching so that thermal shrinkage distortion occurring during the heat development should be eliminated. Such films are described in JP-A-10-48772, JP-A-10-10676, JP-A-10-10677, JP-A-11-65025 and JP-A-11-138648.

[0111] After such a heat treatment, the support preferably shows dimensional changes caused by heating at 120° C. for 30 seconds of −0.03% to +0.01% for the machine direction (MD) and 0 to 0.04% for the transverse direction (TD).

[0112] The photothermographic material of the present invention can be subjected to an antistatic treatment using the conductive metal oxides and/or fluorinated surfactants disclosed in JP-A-11-84573, paragraphs 0040-0051 for the purposes of reducing adhesion of dusts, preventing generation of static marks, preventing transportation failure during the automatic transportation and so forth. As the conductive metal oxides, the conductive acicular tin oxide doped with antimony disclosed in U.S. Pat. No. 5,575,957 and JP-A-11-223901, paragraphs 0012-0020 and the fibrous tin oxide doped with antimony disclosed in JP-A-4-29134 can be preferably used.

[0113] The layer containing a metal oxide should show a surface specific resistance (surface resistivity) of 1012 O or less, preferably 1011 O or less, in an atmosphere at 25° C. and 20% of relative humidity. Such a resistivity provides good antistatic property. Although the surface resistivity is not particularly limited as for the lower limit, it is usually about 107 O.

[0114] The photothermographic material of the present invention preferably has a Beck's smoothness of 2000 seconds or less, more preferably 10 seconds to 2000 seconds, as for at least one of the outermost surfaces of the image-forming layer side and the opposite side, preferably as for the both sides.

[0115] Beck's smoothness referred to in the present invention can be easily determined according to Japanese Industrial Standard (JIS) P8119, “Test Method for Smoothness of Paper and Paperboard by Beck Test Device” and TAPPI Standard Method T479.

[0116] Beck's smoothness of the outermost surfaces of the image-forming layer side and the opposite side of the photothermographic material can be controlled by suitably selecting particle size and amount of matting agent to be contained in the layers constituting the surfaces as described in JP-A-11-84573, paragraphs 0052-0059.

[0117] Optional components of the photothermographic material of the present invention will be explained hereafter.

[0118] The photothermographic material of the present invention may contain a sensitizing dye.

[0119] As a sensitizing dye that can be used for the present invention, there can be advantageously selected those sensitizing dyes that can spectrally sensitize silver halide grains within a desired wavelength range after they are adsorbed by the silver halide grains and have spectral sensitivity suitable for spectral characteristics of the light source to be used for exposure. For example, as dyes that spectrally sensitize in a wavelength range of 550 nm to 750 nm, there can be mentioned the compounds of formula (II) described in JP-A-10-186572, and more specifically, dyes of II-6, II-7, II-14, II-15, II-18, II-23 and II-25 mentioned in the same can be exemplified as preferred dyes. As dyes that spectrally sensitize in a wavelength range of 750 nm to 1400 nm, there can be mentioned the compounds of the formula (I) described in JP-A-11-119374, and more specifically, dyes of (25), (26), (30), (32), (36), (37), (41), (49) and (54) mentioned in the same can be exemplified as preferred dyes. Further, as dyes forming J-band, those disclosed in U.S. Pat. Nos. 5,510,236, 3,871,887 (Example 5), JP-A-2-96131 and JP-A-59-48753 can be exemplified as preferred dyes. These sensitizing dyes can be used each alone, or two or more of them can be used in combination.

[0120] These sensitizing dyes can be added by the method described in JP-A-11-119374, paragraph 0106. However, the method is not particularly limited to this method.

[0121] While the amount of the sensitizing dye used in the present invention may be selected to be a desired amount depending on the performance including sensitivity and fog, it is preferably used in an amount of 10−6 to 1 mole, more preferably 10−4 to 10−1 mole, per mole of silver halide in the photosensitive layer.

[0122] In the present invention, a supersensitizer can be used in order to improve spectral sensitization efficiency. Examples of the supersensitizer used for the present invention include the compounds disclosed in EP-A-587338A, U.S. Pat. Nos. 3,877,943 and 4,873,184, and compounds selected from heteroaromatic or aliphatic mercapto compounds, heteroaromatic disulfide compounds, stilbenes, hydrazines, triazines and so forth.

[0123] Particularly preferred supersensitizers are heteroaromatic mercapto compounds and heteroaromatic disulfide compounds disclosed in JP-A-5-341432, the compounds represented by the formulas (I) and (II) mentioned in JP-A-4-182639, stilbene compounds represented by the formula (I) mentioned in JP-A-10-111543 and the compounds represented by the formula (I) mentioned in JP-A-11-109547. Specifically, there can be mentioned the compounds of M-1 to M-24 mentioned in JP-A-5-341432, the compounds of d-1) to d-14) mentioned in JP-A-4-182639, the compounds of SS-01 to SS-07 mentioned in JP-A-10-111543 and the compounds of 31, 32, 37, 38, 41-45 and 51-53 mentioned in JP-A-11-109547.

[0124] These supersensitizers can be added to the emulsion layer preferably in an amount of 10−4 to 1 mole, more preferably in an amount of 0.001-0.3 mole per mole of silver halide.

[0125] In the photothermographic material the present invention, an acid formed by hydration of diphosphorus pentoxide or a salt thereof is preferably used together as a phosphorus-containing compound. Examples of the acid formed by hydration of diphosphorus pentoxide or a salt thereof include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametaphosphoric acid (salt) and so forth. Particularly preferably used acids formed by hydration of diphosphorus pentoxide or salts thereof are orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific examples of the salt are sodium orthophosphate, sodium dihydrogenorthophosphate, sodium hexametaphosphate, ammonium hexametaphosphate and so forth.

[0126] The acid formed by hydration of diphosphorus pentoxide or a salt thereof that can be preferably used in the present invention is added to the image-forming layer or a binder layer adjacent thereto in order to obtain the desired effect with a small amount of the acid or a salt thereof.

[0127] The phosphorus-containing compound or an acid formed by hydration of diphosphorus pentoxide or a salt thereof may be used in a desired amount (coated amount per m2 of the photothermographic material) depending on the desired performance including sensitivity and fog. However, it can preferably be used in an amount of 0.1-500 mg/m2, more preferably 0.5-100 mg/m2.

[0128] When an additive known as a “toning agent” capable of improving the image is added, the optical density increases in some cases. The toning agent may also be advantageous in forming a black silver image depending on the case. The toning agent is preferably contained in a layer on the side having the image-forming layer in an amount of from 0.1-50 mole %, more preferably from 0.5-20 mole %, per mole of silver. The toning agent may be a so-called precursor that is derived to effectively function only at the time of development.

[0129] For the photothermographic material using a silver salt of an organic acid, toning agents of a wide range can be used. For example, there can be used toning agents disclosed in JP-A-46-6077, JP-A-47-10282, JP-A-49-5019, JP-A-49-5020, JP-A-49-91215, JP-A-50-2524, JP-A-50-32927, JP-A-50-67132, JP-A-50-67641, JP-A-50-114217, JP-A-51-3223, JP-A-51-27923, JP-A-52-14788, JP-A-52-99813, JP-A-53-1020, JP-A-53-76020, JP-A-54-156524, JP-A-54-156525, JP-A-61-183642, JP-A-4-56848, Japanese Patent Publication (Kokoku, hereinafter referred to as JP-B) 49-10727, JP-B-54-20333, U.S. Pat. Nos. 3,080,254, 3,446,648, 3,782,941, 4,123,282 and 4,510,236, British Patent No. 1,380,795, Belgian Patent No. 841910 and so forth. Specific examples of the toning agent include phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-ones and cyclic imides such as quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; naphthalimides such as N-hydroxy-1,8-naphthalimide; cobalt complexes such as cobalt hexaminetrifluoroacetate; mercaptanes such as 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N-(aminomethyl)-aryldicarboxyimides such as N,N-(dimethylaminomethyl)phthalimide and N,N-(dimethylaminomethyl)naphthalene-2,3-dicarboxyimide; blocked pyrazoles, isothiuronium derivatives and a certain kind of photobleaching agents such as N,N′-hexamethylenebis-(1-carbamoyl-3,5-dimethylpyrazole), 1,8-(3,6-diazaoctane)bis-(isothiuroniumtrifluoroacetate) and 2-(tribromomethylsulfonyl)benzothiazole; 3-ethyl-5-[(3-ethyl-2-benzothiazolinylidene)-1-methylethylidene]-2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivatives and metal salts thereof, such as 4-(1-naphthyl)phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone or 2,3-dihydro-1,4-phthalazinedione; combinations of phthalazinone with a phthalic acid derivative (e.g., phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, tetrachlorophthalic acid anhydride); phthalazine, phthalazine derivatives (e.g., 4-(1-naphthyl)phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine, 6-isobutylphthalazine, 6-tert-butylphthalazine, 5,7-dimethylphthalazine, 2,3-dihydrophthalazine) and metal salts thereof; combinations of a phthalazine or derivative thereof and a phthalic acid derivative (e.g., phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, tetrachlorophthalic acid anhydride); quinazolinedione, benzoxazine and naphthoxazine derivatives; rhodium complexes which function not only as a toning agent but also as a halide ion source for the formation of silver halide at the site, such as ammonium hexachlororhodate(III), rhodium bromide, rhodium nitrate and potassium hexachlororhodate(III); inorganic peroxides and persulfates such as ammonium disulfide peroxide and hydrogen peroxide; benzoxazine-2,4-diones such as 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidines and asymmetric triazines such as 2,4-dihydroxpyrimidine and 2-hydroxy-4-aminopyrimidine; azauracil and tetraazapentalene derivatives such as 3,6-dimercapto-1,4-diphenyl-1H,4H-2,3a,5, 6a-tetraazapentalene and 1,4-di(o-chlorophenyl)-3,6-dimercapto-1H,4H-2,3a,5,6a-tetraazapentalene and so forth.

[0130] In the present invention, the phthalazine derivatives represented by the formula (F) mentioned in JP-A-2000-35631 are preferably used as the toning agent. Specifically, A-1 to A-10 mentioned in the same are preferably used.

[0131] The toning agent may be added in any form of a solution, powder, solid microparticle dispersion or the like. The solid microparticle dispersion is performed by using a known pulverization means (e.g., ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill). At the time of solid microparticle dispersion, a dispersion aid may also be used.

[0132] In the photothermographic material of the present invention, it is not preferred that volatile bases such as ammonia exist in the films, since they are likely to be evaporated and evaporated during not only coating process and heat development, but also during storage. The content of NH4+ is preferably 0.06 mmol or less, more preferably 0.03 mmol or less, in terms of the coated amount per 1 m2 of the support. The amount of NH4+ in films was quantified by using an ion chromatography measurement apparatus Type 8000 (according to electric conduction degree method), produced by TOSOH CORP., which was provided with a TSKgel IC-Cation as a separation column and TSK guard column IC-C as a guard column, which were produced by TOSOH CORP. As an eluent, 2 mM nitric acid aqueous solution was used at a flow rate of 1.2 mL/min. The column thermostat temperature was 40° C.

[0133] Extraction of NH4+ from a photosensitive material was attained by immersing the photosensitive material having a size of 1×3.5 cm into 5 mL of extraction solution consisting of a mixture of acetic acid and ion-exchanged water (1:148) for 2 hours and filtering the solution through a 0.45-μm filter, and the measurement was performed for the obtained filtrate.

[0134] For controlling the film surface pH, an organic acid such as phthalic acid derivatives or a nonvolatile acid such as sulfuric acid, and a volatile base such as ammonia are preferably used.

[0135] The photothermographic material of the present invention preferably has a film surface pH of 6.0 or less, more preferably 5.5 or less, before heat development. While it is not particularly limited as for the lower limit, it is normally around 3 or higher.

[0136] A method for measuring the film surface pH is described in JP-A-2000-284399, paragraph 0123.

[0137] In the photothermographic material of the present invention, the silver halide emulsion and/or the silver salt of an organic acid can be further prevented from the production of additional fog or stabilized against the reduction in sensitivity during the stock storage by an antifoggant, a stabilizer or a stabilizer precursor. Examples of suitable antifoggant, stabilizer and stabilizer precursor that can be used individually or in combination include thiazonium salts described in U.S. Pat. Nos. 2,131,038 and 2,694,716, azaindenes described in U.S. Pat. Nos. 2,886,437 and 2,444,605, mercury salts described in U.S. Pat. No. 2,728,663, urazoles described in U.S. Pat. No. 3,287,135, sulfocatechols described in U.S. Pat. No. 3,235,652, oximes, nitrons and nitroindazoles described in British Patent No. 623,448, polyvalent metal salts described in U.S. Pat. No. 2,839,405, thiuronium salts described in U.S. Pat. No. 3,220,839, palladium, platinum and gold salts described in U.S. Pat. Nos. 2,566,263 and 2,597,915, halogen-substituted organic compounds described in U.S. Pat. Nos. 4,108,665 and 4,442,202, triazines described in U.S. Pat. Nos. 4,128,557, 4,137,079, 4,138,365 and 4,459,350, phosphorus compounds described in U.S. Pat. No. 4,411,985 and so forth.

[0138] The photothermographic material of the present invention may contain a benzoic acid compound for the purpose of achieving high sensitivity or preventing fog. The benzoic acid compound for use in the present invention may be any benzoic acid derivative, but preferred examples thereof include the compounds described in U.S. Pat. Nos. 4,784,939 and 4,152,160 and JP-A-9-329863, JP-A-9-329864 and JP-A-9-281637. The benzoic acid compounds may be added to any layer of the photothermographic material, but it is preferably added to a layer on the image-forming layer side with respect to the support, more preferably a layer containing a silver salt of an organic acid. The benzoic acid compound may be added at any step during the preparation of the coating solution. In the case of adding the benzoic acid compound to a layer containing a silver salt of an organic acid, it may be added at any step from the preparation of the silver salt of an organic acid to the preparation of the coating solution, but it is preferably added in the period after the preparation of the silver salt of an organic acid and immediately before the coating. The benzoic acid compound may be added in any form such as powder, solution and microparticle dispersion, or may be added as a solution containing a mixture of the benzoic acid compound with other additives such as a sensitizing dye, reducing agent and toning agent. The benzoic acid compound may be added in any amount. However, the amount thereof is preferably from 1×10−6 to 102 mole, more preferably from 1×10−3 to 0.5 mole, per mole of silver.

[0139] Although not essential for practicing the present invention, it is advantageous in some cases to add a mercury(II) salt as an antifoggant to the image-forming layer. Preferred mercury(II) salts for this purpose are mercury acetate and mercury bromide. The addition amount of mercury for use in the present invention is preferably from 1×10−9 to 1×10−3 mole, more preferably from 1×10−8 to 1×10−4 mole, per mole of coated silver.

[0140] The antifoggant that is particularly preferably used in the present invention is an organic halide, and examples thereof include the compounds described in JP-A-50-119624, JP-A-50-120328, JP-A-51-121332, JP-A-54-58022, JP-A-56-70543, JP-A-56-99335, JP-A-59-90842, JP-A-61-129642, JP-A-62-129845, JP-A-6-208191, JP-A-7-5621, JP-A-7-2781, JP-A-8-15809 and U.S. Pat. Nos. 5,340,712, 5,369,000 and 5,464,737.

[0141] The hydrophilic organic halides represented by the formula (P) mentioned in JP-A-2000-284399 can be preferably used as the antifoggant. Specifically, the compounds (P-1) to (P-118) mentioned in the same are preferably used.

[0142] The amount of the organic halides is preferably 1×1−5 mole to 2 mole/mole Ag, more preferably 5×10−5 mole to 1 mole/mole Ag, further preferably 1×10−4 mole to 5×10−1 mole/mole Ag, in terms of molar amount per mole of Ag (mole/mole Ag). The organic halides may be used each alone, or two or more of them may be used in combination.

[0143] Further, the salicylic acid derivatives represented by the formula (Z) mentioned in JP-A-2000-284399 can be preferably used as the antifoggant. Specifically, the compounds (A-1) to (A-60) mentioned in the same are preferably used. The amount of the salicylic acid represented by the formula (Z) is preferably 1×10−5 mole to 5×10−1 mole/mole Ag, more preferably 5×10−5 mole to 1×10−1 mole/mole Ag, further preferably 1×10−4 mole to 5×10−2 mole/mole Ag, in terms of molar amount per mole of Ag (mole/mole Ag). The salicylic acid derivatives may be used each alone, or two or more of them may be used in combination.

[0144] As antifoggants preferably used in the present invention, formalin scavengers are effective. Examples thereof include the compounds represented by the formula (S) and the exemplary compounds thereof (S-1) to (S-24) mentioned in JP-A-2000-221634.

[0145] The antifoggants used for the present invention may be used after being dissolved in water or an appropriate organic solvent such as alcohols (e.g., methanol, ethanol, propanol, fluorinated alcohol), ketones (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide or methyl cellosolve.

[0146] Further, they may also be used as an emulsion dispersion mechanically prepared according to an already well known emulsion dispersion method by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, ethyl acetate or cyclohexanone as an auxiliary solvent for dissolution. Alternatively, they may be used by dispersing powder of them in water using a ball mill, colloid mill, sand grinder mill, MANTON GAULIN, microfluidizer, or by means of ultrasonic wave according to a known method for solid dispersion.

[0147] While the antifoggants used in the present invention may be added to any layer on the image-forming layer side with respect to the support, that is, the image-forming layer or another layer on that side, they are preferably added to the image-forming layer or a layer adjacent thereto. The image-forming layer is a layer containing a reducible silver salt (silver salt of an organic acid), preferably such a image-forming layer further containing a photosensitive silver halide.

[0148] The photothermographic material of the present invention may contain a mercapto compound, disulfide compound or thione compound so as to control the development by inhibiting or accelerating the development or improve the storability before or after the development.

[0149] Mercapto compounds that can be used in the present invention may have any structure, but those represented by Ar—SM or Ar—S—S—Ar are preferred, wherein M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or condensed aromatic ring containing one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. The heteroaromatic ring is preferably selected from benzimidazole, naphthimidazole, benzothiazole, naphthathiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline and quinazolinone. The heteroaromatic ringmay have a substituent selected from, for example, the group of substituents consisting of a halogen (e.g., Br, Cl), hydroxy, amino, carboxy, alkyl (e.g., alkyl having one or more carbon atoms, preferably from 1-4 carbon atoms), alkoxy (e.g., alkoxy having one or more carbon atoms, preferably from 1-4 carbon atoms) and aryl (which may have a substituent). Examples of the mercapto substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2′-dithiobis (benzothiazole), 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4(3H)-quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 1-phenyl-5-mercaptotetrazole, sodium 3-(5-mercaptotetrazole)benzenesulfonate, N-methyl-N′-{3-(5-mercaptotetrazolyl)phenyl}urea, 2-mercapto-4-phenyloxazole and so forth. However, the present invention is not limited to these.

[0150] The amount of the mercapto compound is preferably from 0.0001-1.0 mole, more preferably from 0.001-0.3 mole, per mole of silver in the image-forming layer.

[0151] A lubricant may be added to the photothermographic material of the present invention.

[0152] A lubricant referred to in the present specification means a compound which, when present on a surface of an object, reduces the friction coefficient of the surface compared with that observed when the compound is absent. The type of the lubricant is not particularly limited.

[0153] Examples of the lubricant that can be used in the present invention include the compounds described in JP-A-11-84573, paragraphs 0061-0064 and JP-A-2000-47083, paragraphs 0049-0062.

[0154] Preferred examples of the lubricant include Cellosol 524 (main component: carnauba wax), Polyron A, 393, H-481 (main component: polyethylene wax), Himicron G-110 (main component: ethylene bisstearic acid amide), Himicron G-270 (main component: stearic acid amide) (all produced by Chukyo Yushi Co., Ltd.),

[0155] W-1: C16H33—O—SO3Na

[0156] W-2: C18H37—O—SO3Na

[0157] and so forth.

[0158] The amount of the lubricant is 0.1-50 weight %, preferably 0.5-30 weight %, of the amount of binder in a layer to which the lubricant is added.

[0159] When such a development apparatus as disclosed in JP-A-2000-171935 or JP-A-2000-47083 is used for the heat development of the photothermographic material of the present invention, in which a photothermographic material is transported in a pre-heating section by facing rollers, and the material is transported in a heat development section by driving force of rollers facing the side of the material having the image-forming layer, while the opposite back surface slides on a smooth surface, ratio of friction coefficients of the outermost surface layer of the side of the photothermographic material having the image-forming layer and the outermost surface layer of the back side is 1.5 or more at the heat development temperature. Although the ratio is not particularly limited as for its upper limit, it is preferably about 30 or less. The value of μb obtained in accordance with the following equation is preferably 1.0 or less, more preferably 0.05-0.8.

[0160] Ratio of friction coefficients =coefficient of dynamic friction between roller material of heat development apparatus and surface of image-forming layer side (μe)/coefficient of dynamic friction between material of smooth surface member of heat development apparatus and back surface (μb)

[0161] In the present invention, the lubricity between the materials of the heat development apparatus and the surface of image-forming layer side and/or the opposite back surface can be controlled by adding a lubricant to the outermost layers and adjusting its addition amount.

[0162] It is preferred that undercoat layers containing a vinylidene chloride copolymer comprising 70 weight % or more of repetition units of vinylidene chloride monomers should be provided on the both surface of the support. Such a vinylidene chloride copolymer is disclosed in JP-A-64-20544, JP-A-1-180537, JP-A-1-209443, JP-A-1-285939, JP-A-1-296243, JP-A-2-24649, JP-A-2-24648, JP-A-2-184844, JP-A-3-109545, JP-A-3-137637, JP-A-3-141346, JP-A-3-141347, JP-A-4-96055, U.S. Pat. No. 4,645,731, JP-A-4-68344, Japanese Patent No. 2,557,641, page 2, right column, line 20 to page 3, right column, line 30, JP-A-2000-39684, paragraphs 0020-0037 and JP-A-2000-47083, paragraphs 0063-0080.

[0163] If the vinylidene chloride monomer content is less than 70 weight %, sufficient moisture resistance cannot be obtained, and dimensional change with time after the heat development will become significant. The vinylidene chloride copolymer preferably contains repetition units of carboxyl group-containing vinyl monomers, besides the repetition units of vinylidene chloride monomer. A polymer consists solely of vinylidene chloride monomers crystallizes, and therefore it becomes difficult to form a uniform film when a moisture resistant layer is coated. Further, carboxyl group-containing vinyl monomers are indispensable for stabilizing the polymer. For these reasons, the repetition units of carboxyl group-containing vinyl monomers are added to the polymer.

[0164] The vinylidene chloride copolymer used in the present invention preferably has a molecular weight of 45,000 or less, more preferably 10,000-45,000, as a weight average molecular weight. When the molecular weight becomes large, adhesion between the vinylidene chloride copolymer layer and the support layer composed of polyester or the like tends to be degraded.

[0165] The content of the vinylidene chloride copolymer used in the present invention is such an amount that the undercoat layers should have a thickness of 0.3 μm or more, preferably 0.3 μm to 4 μm, as a total thickness of the undercoat layers containing the vinylidene chloride copolymer for one side.

[0166] The vinylidene chloride copolymer layer as an undercoat layer is preferably provided a first undercoat layer, which is directly coated on the support, and usually one vinylidene chloride copolymer layer is provided for each side. However, two or more of layers may be provided as the case may be. When multiple layers consisting of two or more layers are provided, the total amount of the vinylidene chloride copolymer is preferably within the range defined above.

[0167] Such layers may contain a crosslinking agent, matting agent or the like, in addition to the vinylidene chloride copolymer.

[0168] The support may be coated with an undercoat layer comprising SBR, polyester, gelatin or the like as a binder, in addition to the vinylidene chloride copolymer layer, as required. The undercoat layer may have a multilayer structure, and may be provided on one side or both sides of the support. The undercoat layer generally has a thickness (per layer) of 0.01-5 μm, more preferably 0.05-1 μm.

[0169] In the present invention, water-soluble polymers are preferably used as a thickener for imparting coating property. The polymers may be either naturally occurring polymers or synthetic polymers, and types thereof are not particularly limited. Specifically, there are mentioned naturally occurring polymers such as starches (corn starch, starch etc.), seaweeds (agar, sodium arginate etc.), vegetable adhesive substances (gum arabic etc.), animal proteins (glue, casein, gelatin, egg white etc.) and adhesive fermentation products (pullulan, dextrin etc.), semi-synthetic polymers such as semi-synthetic starches (soluble starch, carboxyl starch, dextran etc.) and semi-synthetic celluloses (viscose, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose etc.), synthetic polymers such as polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polyvinyl ether, polyethylene-imine, polystyrenesulfonic acid or styrenesulfonic acid copolymer, polyvinylsulfinic acid or vinylsulfinic acid copolymer, polyacrylic acid or acrylic acid copolymer, acrylic acid or acrylic acid copolymer, maleic acid copolymer, maleic acid monoester copolymer and polyacryloylmethyl propanesulfonate or acryloylmethyl propanesulfonate copolymer and so forth.

[0170] Among these, water-soluble polymers preferably used are sodium arginate, gelatin, dextran, dextrin, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, polystyrenesulfonic acid or styrenesulfonic acid copolymer, polyacrylic acid or acrylic acid copolymer, maleic acid monoester copolymer, polyacryloylmethyl propanesulfonate or acryloylmethyl propanesulfonate copolymer, and they are particularly preferably used as a thickener.

[0171] Among these, particularly preferred thickeners are gelatin, dextran, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polystyrenesulfonate or styrenesulfonate copolymer, polyacrylic acid or acrylic acid copolymer, maleic acid monoester copolymer and so forth. These compounds are described in detail in “Shin Suiyosei Polymer no Oyo to Shijo (Applications and Market of Water-soluble Polymers, New Edition)”, CMC Shuppan, Inc., Ed. by Shinji Nagatomo, Nov. 4, 1988.

[0172] The amount of the water-soluble polymers used as a thickener is not particularly limited so long as viscosity is increased when they are added to a coating solution. Their concentration in the solution is generally 0.01-30 weight %, preferably 0.05-20 weight %, particularly preferably 0.1-10 weight %. Viscosity to be increased by the polymers is preferably 1-200 mPa·s, more preferably 5-100 mPa·s, as increased degree of viscosity compared with the initial viscosity. The viscosity is represented by values measured at 25° C. by using a B type rotational viscometer. Upon addition to a coating solution or the like, it is generally desirable that the thickener is added as a solution diluted as much as possible. It is also desirable to perform the addition with sufficient stirring.

[0173] The photothermographic material of the present invention may contain a surfactant.

[0174] Surfactants used in the present invention will be described below. The surfactants used in the present invention are classified into dispersing agents, coating agents, wetting agents, antistatic agents, photographic property controlling agents and so forth depending on the purposes of use thereof, and the purposes can be attained by suitably selecting the surfactants described below and using them. As the surfactants used in the present invention, any of nonionic or ionic (anionic, cationic, betaine) surfactants can be used. Furthermore, fluorinated surfactants can also be preferably used.

[0175] Preferred examples of the nonionic surfactant include surfactants having polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl, sorbitan or the like as the nonionic hydrophilic group. Specifically, there can be mentioned polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene/polyoxypropylene glycols, polyhydric alcohol aliphatic acid partial esters, polyoxyethylene polyhydric alcohol aliphatic acid partial esters, polyoxyethylene aliphatic acid esters, polyglycerin aliphatic acid esters, aliphatic acid diethanolamides, triethanolamine aliphatic acid partial esters and so forth.

[0176] Examples of anionic surfactants include carboxylic acid salts, sulfuric acid salts, sulfonic acid salts and phosphoric acid ester salts. Typical examples thereof are aliphatic acid salts, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfonates, a-olefinsulfonates, dialkylsulfosuccinates, a-sulfonated aliphatic acid salts, N-methyl-N-oleyltaurine, petroleum sulfonates, alkylsulfates, sulfated fats and oils, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styrenylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, naphthalenesulfonate formaldehyde condensates and so forth.

[0177] Examples of the cationic surfactants include amine salts, quaternary ammonium salts, pyridinium salts and so forth, and primary to tertiary amine salts and quaternary ammonium salts (tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridinium salts, alkylimidazolium salts etc.) can be mentioned.

[0178] Examples of betaine type surfactants include carboxybetaine, sulfobetaine and so forth, and N-trialkyl-N-carboxymethylammonium betaine, N-trialkyl-N-sulfoalkyleneammonium betaine and so forth can be mentioned.

[0179] These surfactants are described in Takao Kariyone, “Kaimen Kasseizai no Oyo (Applications of Surfactants”, Saiwai Shobo, Sep. 1, 1980). In the present invention, amount of the surfactant is not particularly limited, and it can be used in an amount providing desired surface activating property. The coating amount of the fluorine-containing surfactant is preferably 0.01-250 mg per 1 m2.

[0180] Specific examples of the surfactants are mentioned below. However, the surfactants are not limited to these (—C6H4— represents phenylene group in the following formulas).

[0181] WA-1: C16H33(OCH2CH2)10OH

[0182] WA-2: C9H19—C6H4—(OCH2CH2)12OH

[0183] WA-3: Sodium dodecylbenzenesulfonate

[0184] WA-4: Sodium tri(isopropyl)naphthalenesulfonate

[0185] WA-5: Sodium tri(isobutyl)naphthalenesulfonate

[0186] WA-6: Sodium dodecylsulfate

[0187] WA-7: a-Sulfasuccinic acid di(2-ethylhexyl) ester sodium salt

[0188] WA-8: C8H17—C6H4—(CH2CH2O)3(CH2)2SO3K

[0189] WA-10: Cetyltrimethylammonium chloride

[0190] WA-11: C11H23CONHCH2CH2N(+)(CH3)2—CH2COO(−)

[0191] WA-12: C8F17SO2N(C3H7)(CH2CH2O)16H

[0192] WA-13: C8F17SO2N(C3H7)CH2COOK

[0193] WA-14: C8F17SO3K

[0194] WA-15: C8F17SO2N(C3H7)(CH2CH2O)4(CH2)4SO3Na

[0195] WA-16: C8F17SO2N(C3H7)(CH2)3OCH2CH2N(+)(CH3)3—CH3.C6H4—SO3(−)

[0196] WA-17: C8F17SO2N(C3H7)CH2CH2CH2N(+)(CH3)2—CH2COO(−)

[0197] Methods for producing the photothermographic material of the present invention and structure of the layers will be explained hereafter.

[0198] The photothermographic material of the present invention has an image-forming layer containing a silver salt of an organic acid, a reducing agent and a photosensitive silver halide on a support, and at least one protective layer is preferably provided on the image-forming layer. Further, the photothermographic material of the present invention preferably has at least one back layer on the side of the support opposite to the side of the image-forming layer (back surface),

[0199] In a preferred embodiment of the present invention, an intermediate layer may be provided as required in addition to the image-forming layer and the protective layer. To improve the productivity or the like, it is preferred that these multiple layers should be simultaneously coated as stacked layers by using aqueous systems. While extrusion coating, slide bead coating, curtain coating and so forth can be mentioned as the coating method, the slide bead coating method shown in JP-A-2000-2964, FIG. 1 is particularly preferred.

[0200] Silver halide photographic photosensitive materials utilizing gelatin as a main binder are rapidly cooled in a first drying zone, which is provided downstream from a coating dye. As a result, the gelatin gels and the coated film is solidified by cooling. The coated film that no longer flows as a result of the solidification by cooling is transferred to a second drying zone, and the solvent in the coating solution is evaporated in this drying zone and subsequent drying zones so that a film is formed. As drying method after the second drying zone, there can be mentioned the air loop method where a support held by rollers is blown by air jet from a U-shaped duct, the helix method (air floating method) where the support is helically wound around a cylindrical duct and dried during transportation and so forth.

[0201] When the layers are formed by using coating solutions comprising polymer latex as a main component of binder, the flow of the coating solution cannot be stopped by rapid cooling. Therefore, the predrying may be insufficient only with the first drying zone. In such a case, if such a drying method as utilized for silver halide photographic photosensitive materials is used, uneven flow or uneven drying may occur, and therefore serious defects are likely to occur on the coated surface.

[0202] The preferred drying method for the present invention is such a method as described in JP-A-2000-2964, where the drying is attained in a horizontal drying zone irrespective of the drying zone, i.e., the first or second drying zone, at least until the constant rate drying is finished. The transportation of the support during the period immediately after the coating and before the support is introduced into the horizontal drying zone may be performed either horizontally or not horizontally, and the rising angle of the material with respect to the horizontal direction of the coating machine may be within the range of 0-70°. Further, in the horizontal drying zone used in the present invention, the support may be transported at an angle within ±15° with respect to the horizontal direction of the coating machine, and it does not mean exactly horizontal transportation.

[0203] The “constant rate drying” referred to in the present specification means a drying process in which all entering calorie is consumed for evaporation of solvent at a constant liquid film temperature. “Decreasing rate drying” referred to in the present specification means a drying process where the drying rate is reduced by various factors (for example, diffusion of moisture in the material for transfer becomes a rate-limiting factor, evaporation surface is recessed etc.) in an end period of the drying, and imparted calorie is also used for increase of liquid film temperature. The critical moisture content for the transition from the constant rate drying to the decreasing rate drying is 200-300%. When the constant rate drying is finished, the drying has sufficiently progressed so that the flowing should be stopped, and therefore such a drying method as used for silver halide photographic photosensitive materials may also be employable. In the present invention, however, it is preferred that the drying should be performed in a horizontal drying zone until the final drying degree is attained even after the constant rate drying.

[0204] As for the drying condition for forming the image-forming layer and/or protective layer, it is preferred that the liquid film surface temperature during the constant rate drying should be higher than minimum film forming temperature (MTF) of polymer latex (MTF of polymer is usually higher than glass transition temperature Tg of the polymer by 3-5° C.). In many cases, it is usually selected from the range of 25-40° C., because of limitations imposed by production facilities. Further, the dry bulb temperature during the decreasing rate drying is preferably lower than Tg of the support (in the case of PET, usually 80° C. or lower). The “liquid film surface temperature” referred to in this specification means a solvent liquid film surface temperature of coated liquid film coated on a support, and the “dry bulb temperature” means a temperature of drying air blow in the drying zone.

[0205] If the constant rate drying is performed under a condition that lowers the liquid film surface temperature, the drying is likely to become insufficient. Therefore, the film-forming property of the protective layer is markedly degraded, and it becomes likely that cracks will be generated on the film surface. Further, film strength also becomes weak and thus it becomes likely that there arise serious problems, for example, the film becomes liable to suffer from scratches during transportation in a light exposure apparatus or heat development apparatus.

[0206] On the other hand, if the drying is performed under a condition that elevates the liquid film surface temperature, the protective layer mainly consisting of polymer latex rapidly becomes a film, but the under layers including the image-forming layer have not lost flowability, and hence it is likely that unevenness is formed on the surface. Furthermore, if the support (base) is subjected to a temperature higher than its Tg, dimensional stability and resistance to curl tendency of the photosensitive material tends to be degraded.

[0207] While the same shall apply to the serial coating, in which an under layer is coated and dried and then an upper layer is coated, as for properties of coating solutions, when an upper layer and a lower layer are coated as stacked layers by coating the upper layer before drying of the lower layer and the both layers are dried simultaneously, in particular, a coating solution for the image-forming layer and a coating solution for protective layer preferably show a pH difference of 2.5 or less, and a smaller value of this pH difference is more preferred. If the pH difference becomes large, it becomes likely that microscopic aggregations are generated at the interface of the coating solutions and thus it becomes likely that serious defects of surface condition such as coating stripes occur during continuous coating for a long length.

[0208] The coating solution for the image-forming layer preferably has a viscosity of 15-100 mPa·S, more preferably 30-70 mPa·S, at 25° C. The coating solution for the protective layer preferably has a viscosity of 5-75 mPa·S, more preferably 20-50 mPa·S, at 25° C. These viscosities are measured by using a B-type viscometer.

[0209] The rolling up after the drying is preferably carried out under conditions of a temperature of 20-30° C. and a relative humidity of 45+20%. As for rolled shape, the material may be rolled so that the surface of the image-forming layer side should be toward the outside or inside of the roll according to a shape suitable for subsequent processing. Further, it is also preferred that, when the material is further processed in a rolled shape, the material should be rolled up into a shape of roll in which the sides are reversed compared with the original rolled shape during processing, in order to eliminate the curl generated while the material is in the original rolled shape. Relative humidity of the photosensitive material is preferably controlled to be in the range of 20-55% (measured at 25° C.).

[0210] In conventional coating solutions for photographic emulsions, which are viscous solutions containing silver halide and gelatin as a base, air bubbles are dissolved in the solutions and eliminated only by feeding the solution by pressurization, and air bubbles are scarcely formed even when the solutions are placed under atmospheric pressure again for coating. However, as for the coating solution for the image-forming layer containing dispersion of silver salt of organic acid, polymer latex and so forth preferably used in the present invention, only feeding of it by pressurization is likely to result in insufficient degassing. Therefore, it is preferably fed so that air/liquid interfaces should not be produced, while giving ultrasonic vibration to perform degassing.

[0211] In the present invention, the degassing of a coating solution is preferably performed by a method where the coating solution is degassed under reduced pressure before coating, and further the solution is maintained in a pressurized state at a pressure of 1.5 kg/cm2 or more and continuously fed so that air/liquid interfaces should not be formed, while giving ultrasonic vibration to the solution. Specifically, the method disclosed in JP-B-55-6405 (from page 4, line 20 to page 7, line 11) is preferred. As an apparatus for performing such degassing, the apparatus disclosed in JP-A-2000-98534, examples and FIG. 2 is preferably used.

[0212] The pressurization condition is preferably 1.5 kg/cm2 or more, more preferably 1.8 kg/cm2 or more. While the pressure is not particularly limited as for its upper limit, it is usually about 5 kg/cm2 or less. Ultrasonic wave given to the solution should have a sound pressure of 0.2 V or more, preferably 0.5 V to 3.0 V. Although a higher sound pressure is generally preferred, an unduly high sound pressure provides high temperature portions due to cavitation, which may cause fogging. While frequency of the ultrasonic wave is not particularly limited, it is usually 10 kHz or higher, preferably 20 kHz to 200 kHz. The degassing under reduced pressure means a process where a coating solution is placed in a sealed tank (usually a tank in which the solution is prepared or stored) under reduced pressure to increase diameters of air bubbles in the coating solution so that degassing should be attained by buoyancy imparted to the air bubbles. The reduced pressure condition for the degassing under reduced pressure is −200 mmHg or a pressure condition lower than that, preferably −250 mmHg or a pressure condition lower than that. Although the lower limit of the pressure condition is not particularly limited, it is usually about −800 mmHg or higher. Time under the reduced pressure is 30 minutes or more, preferably 45 minutes or more, and its upper limit is not particularly limited.

[0213] In the present invention, the image-forming layer, protective layer for the image-forming layer, undercoat layer and back layer may contain a dye in order to prevent halation and so forth as disclosed in JP-A-11-84573, paragraphs 0204-0208 and JP-A-2000-47083, paragraphs 0240-0241.

[0214] Various dyes and pigments can be used for the image-forming layer for improvement of color tone and prevention of irradiation. While arbitrary dyes and pigments may be used for the image-forming layer, the compounds disclosed in JP-A-11-119374, paragraphs 0297, for example, can be used. These dyes may be added in any form such as solution, emulsion, solid microparticle dispersion and macromolecule mordant mordanted with the dyes. Although the amount of these compounds is determined by the desired absorption, they are preferably used in an amount of 1×10−6 g to 1 g per 1 m2, in general.

[0215] When an antihalation dye is used in the present invention, the dye may be any compound so long as it shows intended absorption in a desired range and sufficiently low absorption in the visible region after development, and provides a preferred absorption spectrum pattern of the back layer. For example, the compounds disclosed in JP-A-11-119374, paragraph 0300 can be used. There can also be used a method of reducing density obtained with a dye by thermal decoloration as disclosed in Belgian Patent No. 733,706, a method of reducing the density by decoloration utilizing light irradiation as disclosed in JP-A-54-17833 and so forth.

[0216] When the photothermographic material of the present invention after heat development is used as a mask for the production of printing plate from a PS plate, the photothermographic material after heat development carries information for setting up light exposure conditions of platemaking machine for PS plates or information for setting up platemaking conditions including transportation conditions of mask originals and PS plates as image information. Therefore, in order to read such information, densities (amounts) of the aforementioned irradiation dye, halation dye and filter dye are limited. Because the information is read by using LED or laser, Dmin (minimum density) in a wavelength region of the sensor must be low, i.e., the absorbance must be 0.3 or less. For example, a platemaking machine S-FNRIII produced by Fuji Photo Film Co., Ltd. uses a light source having a wavelength of 670 nm for a detector for detecting resister marks and a bar code reader. Further, platemaking machines of APML series produced by Shimizu Seisaku Co., Ltd. utilize a light source at 670 nm as a bar code reader. That is, if Dmin (minimum density) around 670 nm is high, the information on the film cannot be correctly detected, and thus operation errors such as transportation failure, light exposure failure and so forth are caused in platemaking machines. Therefore, in order to read information with a light source of 670 nm, Dmin around 670 nm must be low and the absorbance at 660-680 nm after the heat development must be 0.3 or less, more preferably 0.25 or less. Although the absorbance is not particularly limited as for its lower limit, it is usually about 0.10.

[0217] Light exposure and heat development of the photothermographic material of the present invention will be explained hereafter.

[0218] In the present invention, as the exposure apparatus used for the imagewise light exposing, any apparatus may be used so long as it is an exposure apparatus enabling light exposure with an exposure time of 10−6 second or shorter. However, a light exposure apparatus utilizing a laser diode (LD) or a light emitting diode (LED) as a light source is preferably used in general. In particular, LD is more preferred in view of high output and high resolution. Any of these light sources may be used so long as they can emit a light of electromagnetic wave spectrum of desired wavelength range. For example, as for LD, dye lasers, gas lasers, solid state lasers, semiconductor lasers and so forth can be used.

[0219] The light exposure in the present invention is performed with overlapped light beams of light sources. The term “overlapped” means that a vertical scanning pitch width is smaller than the diameter of the beams. For example, the overlap can be quantitatively expressed as FWHM/vertical-scanning pitch width (overlap coefficient), where the beam diameter is represented as a half width of beam strength (FWHM). In the present invention, it is preferred that this overlap coefficient is 0.2 or more.

[0220] The scanning method of the light source of the light exposure apparatus used in the present invention is not particularly limited, and the cylinder external surface scanning method, cylinder internal surface scanning method, flat surface scanning method and so forth can be used. Although the channel of light source may be either single channel or multichannel, a multichannel comprising two or more of laser heads is preferred, because it provides high output and shortens writing time. In particular, for the cylinder external surface scanning method, a multichannel carrying several to several tens or more of laser heads is preferably used.

[0221] The photothermographic material of the present invention shows low haze upon the light exposure, and therefore it is likely to generate interference fringes. As techniques for preventing such interference fringes, there are known a technique of obliquely irradiating a photosensitive material with a laser light as disclosed in JP-A-5-113548, a technique of utilizing a multimode laser as disclosed in WO95/31754 and so forth, and these techniques are preferably used.

[0222] Although any method may be used as the heat development process of the photothermographic material of the present invention, the development is usually performed by heating a photothermographic material exposed imagewise. As preferred embodiments of heat development apparatus to be used, there are heat development apparatuses in which a photothermographic material is brought into contact with a heat source such as heat roller or heat drum as disclosed in JP-B-5-56499, JP-A-9-292695, JP-A-9-297385 and WO95/30934, and heat development apparatuses of non-contact type as disclosed in JP-A-7-13294, WO97/28489, WO97/28488 and WO97/28487. Particularly preferred embodiments are the heat development apparatuses of non-contact type. The temperature for the development is preferably 80° C. to 250° C., more preferably 100° C. to 140° C. The development time is preferably 1-180 seconds, more preferably 5-90 seconds. The line speed is preferably 140 cm/minute or more, more preferably 150 cm/minute or more.

[0223] As a method for preventing uneven development due to dimensional change of the photothermographic material during the heat development, it is effective to employ a method for forming images wherein the material is heated at a temperature of 80° C. or higher but lower than 115° C. for 5 seconds or more so as not to develop images, and then subjected to heat development at 110-140° C. to form images (so-called multi-step heating method).

[0224] Since the photothermographic material of the present invention is subjected to a high temperature of 110° C. or higher during the heat development, a part of the components contained in the material or a part of decomposition products produced by the heat development are volatilized. It is known that these volatilized components exert various bad influences, for example, they may cause uneven development, erode structural members of development apparatuses, deposit at low temperature portions as dusts to cause deformation of image surface, adhere to image surface as stains and so forth. As a method for eliminating these influences, it is known to provide a filter on the heat development apparatus, or suitably control air flows in the heat development apparatus. These methods may be effectively used in combination.

[0225] WO95/30933, WO97/21150 and International Patent Publication in Japanese (Kohyo) No. 10-500496 disclose use of a filter cartridge containing binding absorption particles and having a first vent for introducing volatilized components and w a second vent for discharging them in heating means for heating a photothermographic material by contact. Further, WO96/12213 and International Patent Publication in Japanese (Kohyo) No. 10-507403 disclose use of a filter consisting of a combination of heat conductive condensation collector and a gas-absorptive microparticle filter. These can be preferably used in the present invention.

[0226] Further, U.S. Pat. No. 4,518,845 and JP-B-3-54331 disclose structures comprising means for eliminating vapor from a film, pressing means for pressing the film to a heat-conductive member and means for heating the heat-conductive member. Further, WO98/27458 discloses elimination of components volatilized from a film and increasing fog from a surface of the film. These techniques are also preferably used for the present invention.

[0227] An example of the structure of heat development apparatus used for the heat development of the photothermographic material of the present invention is shown in FIG. 1. FIG. 1 depicts a side view of a heat development apparatus. The heat development apparatus shown in FIG. 1 comprises carrying-in roller pairs 11 (upper rollers are silicone rubber rollers, and lower rollers are aluminum heating rollers), which carry a photothermographic material 10 into the heating section while making the material in a flat shape and preheating it, and taking-out roller pairs 12, which take out the photothermographic material 10 after heat development from the heating section while maintaining the material to be in a flat shape. The photothermographic material 10 is heat-developed while it is conveyed by the carrying-in roller pairs 11 and then by the taking-out roller pairs 12. Conveying means for carrying the photothermographic material 10 under the heat development is provided with multiple rollers 13 so that they should be contacted with the surface of the image-forming layer side, and a flat surface 14 adhered with non-woven fabric (composed of, for example, aromatic polyamide, Teflon etc.) or the like is provided on the opposite side so that it should be contacted with the back surface. The photothermographic material 10 is conveyed by driving of the multiple rollers 13 contacted with the image-forming layer side, while the back surface slides on the flat surface 14. Heaters 15 are provided over the rollers 13 and under the flat surface 14 so that the photothermographic material 10 should be heated from the both sides. Examples of the heating means include panel heaters and so forth. While clearance between the rollers 13 and the flat surface 14 may vary depending on the material of the flat surface member, it is suitably adjusted to a clearance that allows the conveyance of the photothermographic material 10. The clearance is preferably 0-1 mm.

[0228] The materials of the surfaces of the rollers 13 and the member of the flat surface 14 may be composed of any materials so long as they have heat resistance and they should not cause any troubles in the conveyance of the photothermographic material 10. However, the material of the roller surface is preferably composed of silicone rubber, and the member of the flat surface is preferably composed of non-woven fabric made of aromatic polyamide or Teflon (PTFE). The heating means preferably comprises multiple heaters so that temperature of each heater can be adjusted freely.

[0229] The heating section is constituted by a preheating section A comprising the carrying-in roller pairs 11 and a heat development section B comprising the heaters 15. Temperature of the preheating section A locating upstream from the heat development section B is preferably controlled to be lower than the heat development temperature (for example, lower by about 10-30° C.), and heat development temperature and time are desirably adjusted so that they should be sufficient for evaporating moisture contained in the photothermographic material 10. The temperature is also preferably adjusted to be higher than the glass transition temperature (Tg) of the support of the photothermographic material 10 so that uneven development should be prevented. Temperature distribution of the preheating section and the heat development section is preferably ±1° C. or less, more preferably ±0.5° C. or less.

[0230] Moreover, guide panels 16 are provided downstream from the heat development section B, and they constitute a gradual cooling section C together with the taking-out roller pairs 12.

[0231] The guide panels 16 are preferably composed of a material of low heat conductivity, and it is preferred that the cooling is performed gradually so as not to cause deformation of the photothermographic material 10. The cooling rate is preferably 0.5-10° C./second.

[0232] The heat development apparatus was explained with reference to the example shown in the drawing. However, the apparatus is not limited to the example. For example, the heat development apparatus used for the present invention may have a variety of structures such as one disclosed in JP-A-7-13294. For the multi-stage heating method, which is preferably used for the present invention, the photothermographic material may be successively heated at different temperatures in such an apparatus as mentioned above, which is provided with two or more heat sources at different temperatures.

[0233] The photothermographic material of the present invention is preferably packaged with the packaging material described in JP-A-2000-206653, paragraphs 0014-0026, or the packaging method described in JP-A-2001-13632, paragraphs 0020-0045.

EXAMPLES

[0234] The present invention will be specifically explained with reference to the following examples. The materials, regents, ratios, procedures and so forth shown in the following examples can be optionally changed so long as such change does not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited by the following examples.

Example 1

[0235] <<Preparation of Silver Halide Emulsion A>>

[0236] In 700 mL of water, 11 g of alkali-treated gelatin (calcium content: 2700 ppm or less), 30 mg of potassium bromide and 1.3 g of sodium 4-methylbenzenesulfonate were dissolved. After the solution was adjusted to pH 6.5 at a temperature of 40° C., 159 mL of an aqueous solution containing 9.3 g of silver nitrate and an aqueous solution containing 1 mol/L of potassium bromide, 5×10−6 mol/L of (NH4)2RhCl5(H2O) and 2×10−5 mol/L of K3IrCl6 were added at such flow rates that silver and the halogen should be added in equal molar numbers with stirring at 600 rpm by means of a stirring blade having a diameter of 25 mm over 2 minutes and 30 seconds. Then, 556 mL of an aqueous solution containing 64.8 g of silver nitrate and a halide salt aqueous solution containing 1 mol/L of potassium bromide and 2×10−5 mol/L of K3IrCl6 were added by the control double jet method over 33 minutes while pAg was maintained at 7.7. Then, the pH was lowered to cause coagulation precipitation to effect desalting, 51.1 g of low molecular weight gelatin having an average molecular weight of 15,000 (calcium content: 20 ppm or less) was added, and pH and pAg were adjusted to 5.9 and 8.0, respectively. The grains obtained were cubic grains having a mean grain size of 0.07 μm, variation coefficient of 13% for projected area and [100] face ratio of 90%.

[0237] The temperature of the silver halide grains obtained as described above was raised to 60° C., and the grains were added with 76 μmol per mole of silver of sodium benzenethiosulfonate. After 3 minutes, 71 μmol per mole of silver of triethylthiourea was further added, and the grains were ripened for 100 minutes, then added with 5×10−4 mol/L of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 0.17 g of Compound A, and cooled to 40° C.

[0238] Then, while the mixture was maintained at 40° C., it was added with potassium bromide (added as aqueous solution) Sensitizing Dye A mentioned below (added as solution in ethanol) and Compound B mentioned below (added as solution in methanol) were added in amounts of 4.7×10−2 mole, 12.8×10−4 mole and 6.4×10−3 mole, respectively, per mole of the silver halide with stirring. After 20 minutes, the emulsion was quenched to 30° C. to complete the preparation of Silver halide emulsion A.

119

[0239] <<Preparation of Silver Halide Emulsion B>>

[0240] Silver halide emulsion B was obtained in the same manner as in the preparation of Silver halide emulsion A except that 11 g of low molecular weight gelatin having an average molecular weight of 15,000 (calcium content: 20 ppm or less) was added to 700 ml of water instead of 11 g of the alkali-treated gelatin w (calcium content: 2700 ppm or less).

[0241] <<Preparation of Silver Halide Emulsion C>>

[0242] Silver halide emulsion C was obtained in the same manner as in the preparation of Silver halide emulsion B except that the amount of the low molecular weight gelatin having an average molecular weight of 15,000 (calcium content: 20 ppm or less) added to 700 ml of water was increased from 11 g to 22 g, and the amount of the low molecular weight gelatin having an average molecular weight of 15,000 (calcium content: 20 ppm or less) added after coagulation precipitation and desalting was changed from 51.1 g to 45.6 g.

[0243] <<Preparation of Silver Halide Emulsions D and E>>

[0244] Silver halide emulsions D and E were obtained in the same manners as in the preparation of Silver halide emulsions B and C, respectively, except that a stirring blade having a diameter of 50 mm was used instead of the stirring blade having a diameter of 25 mm.

[0245] <<Preparation of Silver Halide Emulsion F>>

[0246] Silver halide emulsion F was obtained in the same manner as in the preparation of Silver halide emulsion B except that the flow rates of 159 mL of the aqueous solution containing 9.3 g of silver nitrate and the aqueous solution containing 1 mol/L of potassium bromide, 5×10−6 mol/L of (NH4)2RhCl5(H2O) and 2×10−5 mol/L of K3IrCl6, which realized addition of equal molar numbers of silver and the halogen, were changed to such flow rates that the molar number of the added halogen should become 1.1 times larger than that of silver.

[0247] <<Preparation of Silver Halide Emulsion G>>

[0248] Silver halide emulsion G was obtained in the same manner as in the preparation of Silver halide emulsion B except that the flow rates of 159 mL of the aqueous solution containing 9.3 g of silver nitrate and the aqueous solution containing 1 mol/L of potassium bromide, 5×10−6 mol/L of (NH4)2RhCl5(H2O) and 2×10−5 mol/L of K3IrCl6, which realized addition of equal molar numbers of silver and halogen, were changed to such flow rates that the molar number of the added silver should become 1.05 times larger than that of the halogen.

[0249] <<Preparation of Silver Halide Emulsion H>>

[0250] Silver halide emulsion H was obtained in the same manner as in the preparation of Silver halide emulsion C except that 2 weight % of low molecular weight gelatin having an average molecular weight of 10,000 (calcium content: 20 ppm or less) was added to the solution containing the halogen.

[0251] <<Preparation of Silver Halide Emulsion I>>

[0252] Silver halide emulsion I was obtained in the same manner as in the preparation of Silver halide emulsion C except that 11 g of low molecular weight gelatin having an average molecular weight of 15,000, 30 mg of potassium bromide and 1.3 g of sodium 4-methylbenzenesulfonate were dissolved in 700 ml of water, and pH was adjusted to 3.0 instead of 6.5 at 40° C.

[0253] <<Preparation of Silver Halide Emulsion J>>

[0254] Silver halide emulsion J was obtained in the same manner as in the preparation of Silver halide emulsion C except that 11 g of low molecular weight gelatin having an average molecular weight of 15,000, 30 mg of potassium bromide and 1.3 g of sodium 4-methylbenzenesulfonate were dissolved in 700 ml of water, and pH was adjusted to 8.0 instead of 6.5 at 40° C.

[0255] <<Preparation of Silver Halide Emulsion K>>

[0256] Silver halide emulsion K was obtained in the same manner as in the preparation of Silver halide emulsion C except that 11 g of low molecular weight gelatin having an average molecular weight of 15,000, 30 mg of potassium bromide and 1.3 g of sodium 4-methylbenzenesulfonate were dissolved in 700 ml of water, and KNO3 was further added in an amount of 0.1 mol/L.

[0257] In an amount of 100 mL each of the aforementioned Emulsions A to K were collected and added with an aqueous solution of silver nitrate and an aqueous solution of potassium bromide at 30° C., and ratio of twin crystals was measured. As a result, the ratios shown in Table 13 mentioned later were obtained.

[0258] <<Preparation of Silver Behenate Dispersion A>>

[0259] In an amount of 87.6 kg of behenic acid (Edenor C22-85R, produced by Henkel Co.), 423 L of distilled water, 49.2 L of 5 mol/L aqueous solution of NaOH and 120 L of tert-butanol were mixed and allowed to react with stirring at 75° C. for one hour to obtain a solution of sodium behenate. Separately, 206.2 L of an aqueous solution containing 40.4 kg of silver nitrate was prepared and kept at 10° C. A mixture of 635 L of distilled water and 30 L of tert-butanol contained in a reaction vessel kept at 30° C. was added with the whole amount of the aforementioned sodium behenate solution and the whole amount of the aqueous silver nitrate solution with stirring at constant flow rates over the periods of 62 minutes and 10 seconds, and 60 minutes, respectively. In this operation, the aqueous silver nitrate solution was added in such a manner that only the aqueous silver nitrate solution should be added for 7 minutes and 20 seconds after starting the addition of the aqueous silver nitrate solution, and then the addition of the aqueous solution of sodium behenate was started and added in such a manner that only the aqueous solution of sodium behenate should be added for 9 minutes and 30 seconds after finishing the addition of the aqueous silver nitrate solution. During the addition, the temperature was controlled so that the temperature in the reaction vessel should be 30° C. and the liquid temperature should not be raised. The piping of the addition system for the sodium behenate solution was warmed by steam trace and the steam amount was controlled so that the liquid temperature at the outlet orifice of the addition nozzle should be 75° C. Further, the piping of the addition system for the aqueous silver nitrate solution was maintained by circulating cold water outside a double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis as the center, and the positions were controlled to be at heights for not contacting with the reaction mixture.

[0260] After finishing the addition of the sodium behenate solution, the mixture was left with stirring for 20 minutes at the same temperature and then the temperature was decreased to 25° C. Thereafter, the solid content was recovered by suction filtration and the solid content was washed with water until electric conductivity of the filtrate became 30 μS/cm. The solid content obtained as described above was stored as a wet cake without being dried.

[0261] When the shape of the obtained silver behenate grains was evaluated by electron microscopic photography, the grains were scaly crystals having a mean diameter of projected areas of 0.52 μm, mean thickness of 0.14 μm and variation coefficient of 15% for mean diameter as spheres.

[0262] Then, dispersion of silver behenate was prepared as follows. To the wet cake corresponding to 100 g of the dry solid content were added 7.4 g of polyvinyl alcohol (PVA-217, produced by Kuraray Co. Ltd., average polymerization degree: about 1700) and water to make the total amount 385 g, and the mixture was pre-dispersed by a homomixer. Then, the pre-dispersed stock dispersion was treated three times by using a dispersing machine (Microfluidizer-M-110S-EH, produced by Microfluidex International Corporation, using G10Z interaction chamber) with a pressure controlled to be 1750 kg/cm2 to obtain Silver behenate dispersion A. During the cooling operation, a desired dispersion temperature was achieved by providing coiled heat exchangers fixed before and after the interaction chamber and controlling the temperature of the refrigerant.

[0263] The silver behenate grains contained in Silver behenate dispersion A obtained as described above were grains having a volume weight average diameter of 0.52 μm and variation coefficient of 15%. The measurement of the grain size was carried out by using Master Sizer X produced by Malvern Instruments Ltd. When the grains were evaluated by electron microscopic photography, the ratio of the long side to the short side was 1.5, the grain thickness was 0.14 μm, and the mean aspect ratio (ratio of diameter as circle of projected area of grain and grain thickness) was 5.1.

[0264] The obtained Silver behenate dispersion A was used for the preparation of the coating solution described below.

[0265] <<Preparation of Solid Microparticle Dispersion of Reducing Agent>>

[0266] In an amount of 10 kg of reducing agent [1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane] and 10 kg of 20 weight % aqueous solution of denatured polyvinyl alcohol (Poval MP203, produced by Kuraray Co. Ltd.) were added with 400 g of Safinol 104E (Nisshin Kagaku Co.), 640 g of methanol and 16 kg of water, and mixed sufficiently to form slurry. The slurry was fed by a diaphragm pump to a bead mill of horizontal type (UVM-2, produced by Imex Co.) containing zirconia beads having a mean diameter of 0.5 mm, and dispersed for 3 hours and 30 minutes. Then, the slurry was added with 4 g of benzoisothiazolinone sodium salt and water so that the concentration of the reducing agent should become 25 weight % to obtain a solid microparticle dispersion of reducing agent. The reducing agent particles contained in the obtained dispersion had a median diameter of 0.44 μm, maximum particle diameter of 2.0 μm or less and variation coefficient of 19% for mean particle diameter. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove dusts and so forth, and used for the preparation of the coating solution described below.

[0267] <<Preparation of Solid Microparticle Dispersion of Organic Polyhalogenated Compound A>>

[0268] In an amount of 10 kg of Organic polyhalogenated compound A mentioned below [tribromomethyl(4-(2,4,6-trimethylphenylsulfonyl)phenyl) sulfone], 10 kg of 20 weight % aqueous solution of denatured polyvinyl alcohol (Poval MP203, produced by Kuraray Co. Ltd.), 639 g of 20 weight % aqueous solution of sodium triisopropylnaphthalenesulfonate, 400 g of Safinol 104E (Nisshin Kagaku Co.), 640 g of methanol and 16 kg of water were mixed sufficiently to form slurry. The slurry was fed by a diaphragm pump to a bead mill of horizontal type (UVM-2, produced by Imex Co.) containing zirconia beads having a mean diameter of 0.5 mm, and dispersed for 5 hours. Then, the slurry was added with water so that the concentration of Organic polyhalogenated compound A should become 25 weight % to obtain solid microparticle dispersion of Organic polyhalogenated compound A. The particles of the organic polyhalogenated compound contained in the obtained dispersion had a median diameter of 0.36 μm, maximumparticle diameter of 2.0 μm or less and variation coefficient of 18% for mean particle diameter. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove dusts and so forth, and used for the preparation of the coating solution described below.

[0269] <<Preparation of Solid Microparticle Dispersion of Organic Polyhalogenated Compound B>>

[0270] In an amount of 5 kg of Organic polyhalogenated compound B mentioned below [tribromomethylnaphthylsulfone], 2.5 kg of 20 weight % aqueous solution of denatured polyvinyl alcohol (Poval MP203, produced by Kuraray Co. Ltd.), 213 g of 20 weight % aqueous solution of sodium triisopropylnaphthalenesulfonate and 10 kg of water were mixed sufficiently to form slurry. The slurry was fed by a diaphragm pump to a bead mill of horizontal type (UVM-2, produced by Imex Co.) containing zirconia beads having a mean diameter of 0.5 mm, and dispersed for 5 hours. Then, the slurry was added with 2.5 g of benzoisothiazolinone sodium salt and water so that the concentration of Organic polyhalogenated compound B should become 23.5 weight % to obtain solid microparticle dispersion of Organic polyhalogenated compound B. The particles of the organic polyhalogenated compound contained in the obtained dispersion had a median diameter of 0.38 μm, maximum particle diameter of 2.0 μm or less and variation coefficient of 20% for mean particle diameter. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove dusts and so forth, and used for the preparation of the coating solution described below.

[0271] <<Preparation of Aqueous Solution of Organic Polyhalogenated Compound C>>

[0272] In an amount of 75.0 mL of water, 8.6 mL of 20 weight % aqueous solution of sodium triisopropylnaphthalenesulfonate, 6.8 mL of 5 weight % aqueous solution of sodium dihydrogenorthophosphate dihydrate and 9.5 mL of 1 mol/L aqueous solution of potassium hydroxide were successively added at room temperature with stirring, and the mixture was stirred for 5 minutes after the addition was completed. Further, the mixture was added with 4.0 g of Organic polyhalogenated compound C mentioned below [3-tribromomethanesulfonylbenzoylaminoacetic acid] as powder and it was uniformly dissolved to obtain 100 mL of transparent aqueous solution of Organic polyhalogenated compound C. The obtained aqueous solution was filtered through a polyester screen of 200 mesh to remove dusts and so forth, and used for the preparation of the coating solution described below.

[0273] <<Preparation of Emulsion Dispersion of Compound Z>>

[0274] In an amount of 10 kg of R-054 (Sanko Co., Ltd.) containing 85 weight % of Compound Z mentioned below was mixed with 11.66 kg of MIBK and dissolved in the solvent and dissolved at 80° C. for 1 hour in an atmosphere substituted with nitrogen. This solution was added with 25.52 kg of water, 12.76 kg of 20 weight % aqueous solution of MP polymer (MP-203, produced by Kuraray Co. Ltd.) and 0.44 kg of 20 weight % aqueous solution of sodium triisopropylnaphthalenesulfonate and subjected to emulsion dispersion at 20-40° C. and 3600 rpm for 60 minutes. The dispersion was further added with 0.08 kg of Safinol 104E (Nisshin Kagaku Co.) and 47.94 kg of water and distilled under reduced pressure to remove MIBK. Then, the concentration of Compound Z was adjusted to 10 weight %. The particles of Compound Z contained in the dispersion obtained as described above had a median diameter of 0.19 μm, maximum particle diameter of 1.5 μm or less and variation coefficient of 17% for mean particle diameter. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove dusts and so forth and used for the preparation of the coating solution described below.

[0275] <<Preparation of Dispersion of 6-Isopropylphthalazine Compound>>

[0276] In an amount of 62.35 g of water was added with 2.0 g of denatured polyvinyl alcohol (Poval MP203, produced by Kuraray Co., Ltd.) with stirring so that the denatured polyvinyl alcohol should not coagulate, and mixed by stirring for 10 minutes. Then, the mixture was heated until the internal temperature reached 50° C., and stirred for 90 minutes at an internal temperature in the range of 50-60° C. to attain uniform dissolution. The internal temperature was lowered to 40° C. or lower, and the mixture was added with 25.5 g of 10 weight % aqueous solution of polyvinyl alcohol (PVA-217, produced by Kuraray Co., Ltd.), 3.0 g of 20 weight % aqueous solution of sodium triisopropylnaphthalenesulfonate and 7.15 g of 70% aqueous solution of 6-isopropylphthalazine and stirred for 30 minutes to obtain 100 g of transparent dispersion. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove dusts and so forth, and used for the preparation of the coating solution described below.

[0277] <<Preparation of Solid Microparticle Dispersion of High Contrast Agent>>

[0278] In an amount of 4 kg of Compound XX-1 mentioned below was added with 1 kg of polyvinyl alcohol (Poval PVA-217, produced by Kuraray Co., Ltd.) and 36 kg of water, and mixed sufficiently to form slurry. The slurry was fed by a diaphragm pump to a bead mill of horizontal type (UVM-2, produced by Imex Co.) containing zirconia beads having a mean diameter of 0.5 mm, and dispersed for 12 hours. Then, the slurry was added with 4 g of benzoisothiazolinone sodium salt and water so that the concentration of the nucleating agent should become 10 weight % to obtain solid microparticle dispersion of Compound XX-1 mentioned below. The particles of the nucleating agent contained in the dispersion obtained as described above had a median diameter of 0.34 μm, maximum particle diameter of 3.0 μm or less, and variation coefficient of 19% for the mean particle diameter. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove dusts and so forth, and used for the preparation of the coating solution described below.

[0279] <<Preparation of Solid Microparticle Dispersion of Development Accelerator W>>

[0280] In an amount of 10 kg of Development accelerator W mentioned below, 10 kg of 20 weight % aqueous solution of denatured polyvinyl alcohol (Poval MP203, produced by Kuraray Co., Ltd.) and 20 kg of water were added and mixed sufficiently to form slurry. The slurry was fed by a diaphragm pump to a bead mill of horizontal type (UVM-2, produced by Imex Co.) containing zirconia beads having a mean diameter of 0.5 mm, and dispersed for 5 hours. Then, the slurry was added with water so that the concentration of Development accelerator W should become 20 weight % to obtain a microparticle dispersion of Development accelerator W. The particles of the development accelerator contained in the dispersion obtained as described above had a median diameter of 0.5 μm, maximum particle diameter of 2.0 μm or less, and variation coefficient of 18% for the mean particle diameter. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove dusts and so forth, and used for the preparation of the coating solution described below.

[0281] <<Preparation of Coating Solution for Image-Forming Layer>>

[0282] Silver behenate dispersion A prepared above was added with the following binder, components and each silver halide emulsion in the indicated amounts per mole of silver in Silver behenate dispersion A, and added with water to prepare a coating solution for image-forming layer. After the completion, the solution was degassed under reduced pressure of 0.54 atm for 45 minutes. The coating solution showed pH of 7.7 and viscosity of 50 mPa·s at 25° C.

2Binder: SBR latex397 g as solid(St/Bu/AA = 68/29/3 (weight %),glass transition temperature: 17° C.(calculated value), Na2S2O8 was usedas polymerization initiator, pH wasadjusted to 6.5 with NH4OH,mean particle diameter: 118 nm)1,1-Bis(2-hydroxy-3,5-dimethyl-149.5 g as solidphenyl)-3,5,5-trimethylhexaneOrganic polyhalogenated compound B36.3 g as solidOrganic polyhalogenated compound C2.34 g as solidSodium ethylthiosulfonate0.47 gBenzotriazole1.02 gPolyvinyl alcohol (PVA-235, produced10.8 gby Kuraray Co., Ltd.)6-Isopropylphthalazine16.0 gCompound Z9.7 g as solidCompound XX-112.7 gDye AAmount giving(added as a mixture with lowopticalmolecular weight gelatin havingdensity ofmean molecular weight of 15,000)0.3 at 783 nm(about 0.40 gas solid)Silver halide emulsion shown0.06 mole as Agin Table 13Compound A mentioned below40 ppm in the coatingas preservativesolution (2.5 mg/m2as coated amount)Methanol1 weight % as to totalsolvent amount in thecoating solutionEthanol2 weight % as to totalsolvent amount in thecoating solutionpH was adjusted by using NaOH as a pH adjusting agent. (The coated film showed a glass transition temperature of 17° C.) Polyhalogenated compound A

120

Polyhalogenated compound B

121

Compound Z

122

Polyhalogenated compound C

123

Dye A

124

Development accelerator W

125

Compound XX-1

126

[0283] <<Preparation of Coating Solution for Protective Layer>>

[0284] In an amount of 943 g of a polymer latex solution of copolymer of methyl methacrylate/styrene/2-ethylhexyl acrylate/2-hydroxyethyl methacrylate/acrylic acid=58.9/8.6/25.4/5.1/2 (weight %) (glass transition temperature as copolymer: 46° C. (calculatedvalue), solid content: 21.5 weight %, the solution contained 100 ppm of Compound A and further contained Compound D mentioned below as a film-forming aid in an amount of 15 weight % relative to solid content of the latex so that the glass transition temperature of the coating solution should become 24° C., mean particle diameter: 116 nm) was added with water, 1.62 g of Compound E mentioned below, 114.8 g of the aqueous solution of Organic polyhalogenated compound C, 10.0 g as solid content of Organic polyhalogenated compound A, 0.69 g as solid content of sodium dihydrogenorthophosphate dihydrate, 11.55 g as solid content of Development accelerator A, 1.58 g of matting agent (polystyrene particles, mean particle diameter: 7 μm, variation coefficient of 8% for mean particle diameter) and 29.3 g of polyvinyl alcohol (PVA-235, Kuraray Co., Ltd.), and further added with water to form a coating solution (containing 0.8 weight % of methanol solvent). After the preparation, the solution was degassed under reduced pressure of 0.47 atm for 60 minutes. The obtained coating solution for protective layer showed pH of 5.5 and viscosity of 45 mPa·s at 25° C.

[0285] <<Preparation of Coating Solution for Lower Overcoat Layer>>

[0286] In an amount of 625 g of a polymer latex solution of copolymer of methyl methacrylate/styrene/2-ethylhexyl acrylate/2-hydroxyethyl methacrylate/acrylic acid=58.9/8.6/25.4/5.1/2 (weight %) (glass transition temperature as copolymer: 46° C. (calculatedvalue), solid content: 21.5 weight %, the solution contained 100 ppm of Compound A and further contained Compound D as a film-forming aid in an amount of 15 weight % relative to solid content of the latex so that the glass transition temperature of the coating solution should become 24° C., mean particle diameter: 74 nm) was added with water, 0.23 g of Compound C mentioned below, 0.13 g of Compound E mentioned below, 11.7 g of Compound F mentioned below, 2.7 g of Compound H mentioned below and 11.5 g of polyvinyl alcohol (PVA-235, Kuraray Co., Ltd.), and further added with water to form a coating solution (containing 0.1 weight % of methanol solvent). After the preparation, the solution was degassed under reduced pressure of 0.47 atm for 60 minutes. The obtained coating solution for lower overcoat layer showed pH of 2.6 and viscosity of 30 mPa·s at 25° C.

[0287] <<Preparation of Coating Solution for Upper Overcoat Layer>>

[0288] In an amount of 649 g of polymer latex solution of copolymer of methyl methacrylate/styrene/2-ethylhexyl acrylate/2-hydroxyethyl methacrylate/acrylic acid=58.9/8.6/25.4/5.1/2 (weight %) (glass transition temperature of the copolymer: 46° C. (calculated value), solid content: 21.5 weight %, the solution contained Compound A at a concentration of 100 ppm and further containing Compound D as a film-forming aid in an amount of 15 weight % relative to solid content of the latex so that the glass transition temperature of coating solution should become 24° C., mean particle diameter: 116 nm) was added with water, 18.4 g of 30 weight % solution of carnauba wax (Cellosol 524, Chukyo Yushi Co., Ltd., silicone content: less than 5 ppm), 0.23 g of Compound C, 1.85 g of Compound E, 1.0 g of Compound G mentioned below, 3.45 g of matting agent (polystyrene particles, mean diameter: 7 μm, variation coefficient for mean particle diamter: 8%) and 26.5 g of polyvinyl alcohol (PVA-235, Kuraray Co., Ltd.) and further added with water to form a coating solution (containing 1.1 weight % of methanol solvent). After the preparation, the coating solution was degassed at a reduced pressure of 0.47 atm for 60 minutes. The obtained coating solution for upper overcoate layer showed pH of 5.3 and viscosity of 25 mPa·s at 25° C.

127

[0289] <<Preparation of Polyethylene Terephthalate (PET) Support with Back Layers and Undercoat Layers>>

[0290] (1) Preparation of PET Support

[0291] PET having IV (intrinsic viscosity) of 0.66 (measured in phenol/tetrachloroethane=6/4 (weight ratio) at 25° C.) was obtained in a conventional manner by using terephthalic acid and ethylene glycol. The product was pelletized, dried at 130° C. for 4 hours, then melted at 300° C., extruded from a T-die and rapidly cooled to form an unstretched film having such a thickness that the thickness should become 120 μm after thermal fixation.

[0292] The film was stretched along the longitudinal direction by 3.3 times at 110° C. using rollers of different peripheral speeds, and then stretched along the transverse direction by 4.5 times at 130° C. using a tenter. Then, the film was subjected to thermal fixation at 240° C. for 20 seconds, and relaxed by 4% along the transverse direction at the same temperature. Then, the chuck of the tenter was released, the both edges of the film were knurled, and the film was rolled up at 4.8 kg/cm2. Thus, a roll of a PET support having a width of 2.4 m, length of 3500 m and thickness of 120 μm was obtained.

[0293] (2) Preparation of Undercoat Layers and Back Layers

[0294] (i) First Undercoat Layer

[0295] The aforementioned PET support was subjected to a corona discharge treatment of 0.375 kV·A·minute/m2, then coated with a coating solution having the following composition in an amount of 6.2 mL/m2, and dried at 125° C. for 30 seconds, 150° C. for 30 seconds, and 185° C. for 30 seconds.

3Latex A mentioned below280gKOH0.5gPolystyrene microparticles0.03g(mean particle diameter: 2 μm,variation coefficient of 7%for mean particle diameter)2,4-Dichloro-6-hydroxy-s-triazine1.8gCompound Bc-C mentioned below0.097gDistilled waterAmount givingtotal weight of1000g

[0296] Latex A

[0297] Core/shell type latex comprising 90 weight % of core and 10 weight % of shell,

[0298] Core: vinylidene chloride/methyl acrylate/methyl methacrylate/acrylonitrile/acrylic acid=93/3/3/0.9/0.1 (weight %),

[0299] Shell: vinylidene chloride/methyl acrylate/methyl methacrylate/acrylonitrile/acrylic acid=88/3/3/3/3 (weight %),

[0300] Weight average molecular weight: 38000

[0301] (ii) Second Undercoat Layer

[0302] A coating solution having the following composition was coated on the first undercoat layer in an amount of 5.5 mL/m2 and dried at 125° C. for 30 seconds, 150° C. for 30 seconds, and 170° C. for 30 seconds.

4Deionized gelatin10g(Ca2+ content: 0.6 ppm,jelly strength: 230 g)Acetic acid10g(20 weight % aqueous solution)Compound Bc-A mentioned below0.04gMethyl cellulose25g(2 weight % aqueous solution)Polyethyleneoxy compound0.3gDistilled waterAmount givingtotal weight of1000g

[0303] (iii) First Back Layer

[0304] The surface of the support opposite to the surface coated with the undercoat layers was subjected to a corona discharge treatment of 0.375 kV·A·minute/m2, coated with a coating solution having the following composition in an amount of 13.8 mL/m2, and dried at 125° C. for 30 seconds, 150° C. for 30 seconds, and 185° C. for 30 seconds.

5Julimer ET-41023g(30 weight % aqueous dispersionNihon Junyaku Co., Ltd.)Alkali-treated gelatin4.44g(molecular weight: about 10,000,Ca2+ content: 30 ppm)Deionized gelatin0.84g(Ca2+ content: 0.6 ppm)Compound Bc-A0.02gDye Bc-A mentioned belowAmount givingoptical densityof 1.3-1.4 at783 nm, about0.88gPolyoxyethylene phenyl ether1.7gWater-soluble melamine compound15g(Sumitex Resin M-3, SumitomoChemical Co., Ltd., 8 weight %aqueous solution)Aqueous dispersion of Sb-doped24gSbO2 acicular grains (FS-10D,Ishihara Sangyo Kaisha, Ltd.)Polystyrene microparticles0.03g(mean diameter: 2.0 μm,variation coefficient of 7%for mean particle diameter)Distilled waterAmount givingtotal weight of1000g

[0305] (iv) Second Back Layer

[0306] A coating solution having the following composition was coated on the first back layer in an amount of 5.5 mL/m2 and dried at 125° C. for 30 seconds, 150° C. for 30 seconds, and 170° C. for 30 seconds.

6Julimer ET-41057.5g(30 weight % aqueous dispersionNihon Junyaku Co., Ltd.)Polyoxyethylene phenyl ether1.7gWater-soluble melamine compound15g(Sumitex Resin M-3, SumitomoChemical Co., Ltd., 8 weight %aqueous solution)Cellosol 5246.6g(30 weight % aqueous solution,Chukyo Yushi Co., Ltd.)Distilled waterAmount givingtotal weight of1000g

[0307] (v) Third Back Layer

[0308] The same coating solution as the first undercoat layer was coated on the second back layer in an amount of 6.2 mL/m2 and dried at 125° C. for 30 seconds, 150° C. for 30 seconds, and 185° C. for 30 seconds.

[0309] (vi) Fourth Back Layer

[0310] A coating solution having the following composition was coated on the third back layer in an amount of 13.8 mL/m2 and dried at 125° C. for 30 seconds, 150° C. for 30 seconds, and 170° C. for 30 seconds.

7Latex B mentioned below286gCompound Bc-B mentioned below2.7gCompound Bc-C mentioned below0.6gCompound Bc-D mentioned below0.5g2,4-Dichloro-6-hydroxy-s-triazine2.5gPolymethyl methacrylate7.7g(10 weight % aqueous dispersion,mean particle diameter: 5 μm,variation coefficient of 7%for mean particle diameter)Distilled waterAmount givingtotal weight of1000g

[0311] Latex B

[0312] Latex of copolymer of methyl methacrylate/styrene/2-ethylhexyl acrylate/2-hydroxyethyl methacrylate/acrylic acid=59/9/26/5/1 (weight %)

128

[0313] (3) Heat Treatment During Transportation

[0314] (3-1) Heat Treatment

[0315] The PET support with back layers and undercoat layers prepared as described above was introduced into a heat treatment zone having a total length of 200 m set at 160° C., and transported at a tension of 2 kg/cm2 and a transportation speed of 20 m/minute.

[0316] (3-2) Post-Heat Treatment

[0317] Following the aforementioned heat treatment, the support was subjected to a post-heat treatment by passing it through a zone at 40° C. for 15 seconds, and rolled up. The rolling up tension for this operation was 10 kg/cm2.

[0318] <<Preparation of Photothermographic Material>>

[0319] On the second undercoat layer of the PET support, the aforementioned coating solution for image-forming layer was coated so that the coated silver amount should become 1.5 g/m2 by the slide bead method disclosed in JP-A-2000-2964, FIG. 1. On the image-forming layer, the aforementioned coating solution for protective layer was coated simultaneously with the coating solution for image-forming layer as stacked layers so that the coated solid content of the polymer latex should become 1.29 g/m2. Then, the aforementioned coating solution for lower overcoat layer and coating solution for upper overcoat layer were simultaneously coated on the protective layer as stacked layers, so that the coated solid contents of the polymer latex should be 1.97 g/m2 and 1.07 g/m2, respectively, to prepare a photothermographic material.

[0320] After the coating, the layers were dried in a horizontal drying zone (the support was at an angle of 1.5-3′ to the horizontal direction of the coating machine) under the conditions of dew point of 14-25° C. and liquid film surface temperature of 35-40° C. for both of the constant rate drying process and the decreasing rate drying process until it reached around a drying point where flow of coating solutions substantially ceased. After the drying, the material was rolled up under the conditions of a temperature of 23±5° C. and relative humidity of 45±5%. The material was rolled up in such a rolled shape that the image-forming layer side should be exposed to the outside so as to conform to the subsequent processing (image-forming layer outside roll). The relative humidity in the package of the photothermographic material was 20-40% (measured at 25° C.). Each obtained photothermographic material showed a film surface pH of 5.0 and Beck's smoothness of 850 seconds for the image-forming layer side. The opposite surface showed a film surface pH of 5.9 and Beck's smoothness of 560 seconds.

[0321] <<Evaluation of Photographic Performance>>

[0322] Each of the obtained samples was subjected to light exposure through a step wedge using a xenon flash light through an interference filter having a peak at 785 nm for 10-6 second and then subjected to the heat development described below.

[0323] Sensitivity was represented with a reciprocal of exposure giving a density of 1.5 and referred to as S1.5. Photographic sensitivity of Sample No.1-1 was represented as 100 as a relative value. A larger value means higher sensitivity.

[0324] As an index representing contrast of images, y (gradation) was obtained as follows. A point corresponding to fog+density of 0.1 and a point corresponding to fog+density of 1.5 on the characteristic curve were connected with a straight line, and the gradient of this straight line was used as y value. That is, γ is given by an equation: γ=(1.5-0.1)/(log(Exposure giving density of 1.5)−log (Exposure giving density of 0.1)), and a larger γ value means photographic characteristic of higher contrast.

[0325] <<Heat Development>>

[0326] Each light-exposed photothermographic material was heat-developed by using such a heat development apparatus as shown in FIG. 1. The roller surface material of the heat development section was composed of silicone rubber, and the flat surface consisted of Teflon non-woven fabric. The heat development was performed at a transportation line speed of 150 cm/minute in the preheating section for 12.2 seconds (driving units of the preheating section and the heat development section were independent from each other, and speed difference as to the heat development section was adjusted to −0.5% to −1%, temperatures of each of the metallic rollers and processing times in the preheating section were as follows: first roller, 67° C. for 2.0 seconds; second roller, 82° C. for 2.0 seconds; third roller, 98° C. for 2.0 seconds; fourth roller, 107° C. for 2.0 seconds; fifth roller, 115° C. for 2.0 seconds; and sixth roller, 120° C. for 2.0 seconds), in the heat development section at 120° C. (surface temperature of photothermographic material) for 17.2 seconds, and in the gradual cooling section for 13.6 seconds. The temperature precision as for the transverse direction was ±0.5° C. As for temperature setting of each roller, the temperature precision was secured by using a length of rollers longer than the width of the photothermographic material (for example, width of 61 cm) by 5 cm for the both sides and also heating the protruding portions. Since the rollers showed marked temperature decrease at the both end portions, the temperature of the portions protruding by 5 cm from the ends of the photothermographic material was controlled to be higher than that of the roller center by 1-3° C., so that uniform image density of finished developed image should be obtained for the photothermographic material (for example, within a width of 61 cm).

[0327] <<Evaluation of Practice Density>>

[0328] The obtained photothermographic material was light exposed for 1.2×10−8 second by using a laser light-exposure apparatus of single channel cylindrical internal surface scanning type provided with a semiconductor laser with a beam diameter (½ of FWHMof beam intensity) of 12.56 um, laser output of 50 mW and output wavelength of 783 nm at a mirror revolution number of 60000 rpm. The overlap coefficient of the light exposure was 0.449, and the laser energy density on the photothermographic material surface was 75 μJ/cm2. A test step was output at 175 lines/inch with varying exposure by using the aforementioned laser exposure apparatus. Then, the material was subjected to the heat treatment explained above, and density of a portion showing Dmax (maximum density) obtained with exposure at such an LV value that intermediate dots should account for 50% was measured and used as a practice density.

[0329] Further, Dmin (fog) and Dmax (maximum density) were also evaluated in an environment of 25° C. and relative humidity of 10%. The density measurement was performed by using a Macbeth TD904 densitometer (visible density).

[0330] <<Evaluation of Storability>>

[0331] As for evaluation of storability, the photothermographic material was left at 50° C. and relative humidity of 40% for 4 days (this treatment is referred to as “thermal treatment”), then subjected to the aforementioned light exposure and heat development, and evaluated in a similar manner. Sensitivity variation due to the thermal treatment, ΔS1.5, was represented by a percentage of the sensitivity obtained after the thermal treatment based on the sensitivity obtained before the thermal treatment, which was taken as 100%. A value closer to 100% indicates smaller sensitivity variation.

[0332] The results of the above evaluations for each photothermographic material are shown in Table 13.

8Table 13Relative sensitivityTwin(%)GradationDmincrystalWithWithoutWithWithoutWithWithoutSampleType ofratio ofthermalthermalthermalthermalthermalthermalNo.emulsionemulsiontreatmenttreatmenttreatmenttreatmentDmaxtreatmenttreatmentNote1-1A1.5%1001027.15.53.90.120.14Comparative1-2B0.9%991008.98.04.00.120.13Invention1-3C0.7%99999.39.44.10.120.13Invention1-4D0.2%979910.510.44.20.110.11Invention1-5E0.1%979911.211.14.20.100.10Invention1-6F1.3%1021047.46.13.90.120.14Comparative1-7G1.4%1051106.75.33.80.130.18Comparative1-8H0.5%98999.79.74.10.120.12Invention1-9I0.4%981009.99.94.10.120.12Invention1-10J1.3%1011057.06.33.90.120.14Comparative1-11K0.6%99999.59.54.10.120.12InventionExplanation: Relative sensitivity “with thermal treatment” is a relative sensitivity based onsensitivity of corresponding sample “without thermal treatment”, which is taken as 100%.

[0333] As clearly seen from the results shown in Table 13, the photothermographic materials of the present invention showed low fog as represented by Dmin of 0.10-0.12, and high Dmax (maximum density) of 4.0-4.2. Further, even after the thermal treatment conducted to predict photographic properties after long term storage, they showed little increase of fog as represented by Dmin of 0.1-0.13. Furthermore, they showed little variations of sensitivity and gradation after the thermal treatment.

[0334] From the above, it can be seen that the photothermographic materials of the present invention show low fog and high Dmax not only in usual use but also in use after long term storage.

Example 2

[0335] <<Preparation of Coating Solution for Image-Forming Layer>>

[0336] Silver behenate dispersion A prepared in Example 1 was added with the following binder, components and each of the silver halide emulsion prepared in Example 1 in the indicated amounts per mole of silver in Silver behenate dispersion A, and added with water to prepare a coating solution for image-forming layer. After the preparation, the solution was degassed under reduced pressure of 0.54 atm for 45 minutes. The coating solution showed pH of 7.3-7.7 and viscosity of 40-50 mPa·s at 25° C.

9Binder: SBR latex397 g as solid(St/Bu/AA = 68/29/3 (weight %),glass transition temperature: 17° C.(calculated value), Na2S2O8 was usedas polymerization initiator, pH wasadjusted to 6.5 with NH4OH,mean particle diameter: 118 nm)1,1-Bis(2-hydroxy-3,5-dimethyl-118.2 g as solidphenyl)-3,5,5-trimethylhexaneOrganic polyhalogenated compound A20.0 g as solidOrganic polyhalogenated compound B6.0 g as solidOrganic polyhalogenated compound C2.0 g as solidOrganic polyhalogenated compound D34.4 g as solidmentioned belowDevelopment accelerator W11.5 g as solidSodium ethylthiosulfonate0.3 gBenzotriazole1.2 gPolyvinyl alcohol (PVA-235, produced10.8 gby Kuraray Co., Ltd.)6-Isopropylphthalazine14.0 gCompound Z9.6 g as solidCompound I mentioned below0.2 gCompound XX-2 or XX38.9 gDye AAmount giving(added as a mixture with lowopticalmolecular weight gelatin havingdensity ofmean molecular weight of 15,000)0.3 at 783 nm(about 0.40 gas solid)Silver halide emulsion0.06 mole as AgCompound A as preservative40 ppm in the coatingsolution (2.5 mg/m2as coated amount)Methanol1 weight % as to totalsolvent amount in thecoating solutionEthanol2 weight % as to totalsolvent amount in thecoating solutionNaOH was used as a pH adjusting agent. (The coated film showed a glass transition temperature of 17° C.) Compound XX-2

129

Compound XX-3

130

Compound I

131

Organic polyhalogenated compound C

132

[0337] <<Preparation of Solid Microparticle Dispersion of Organic Polyhalogenated Compound D>>

[0338] In an amount of 6 kg of Organic polyhalogenated compound D, 12 kg of 10 weight % aqueous solution of denatured polyvinyl alcohol (Poval MP203, produced by Kuraray Co. Ltd.), 240 g of 20 weight % aqueous solution of sodium triisopropylnaphthalenesulfonate and 0.18 kg of water were mixed sufficiently to form slurry. The slurry was fed by a diaphragm pump to a bead mill of horizontal type (UVM-2, produced by Imex Co.) containing zirconia beads having a mean diameter of 0.5 mm, and dispersed for 5 hours. Then, the slurry was added with 2 g of benzoisothiazolinone sodium salt and water so that the concentration of Organic polyhalogenated compound D should become 30 weight % to obtain solid microparticle dispersion of Organic polyhalogenated compound D. The particles of the organic polyhalogenated compound contained in the obtained dispersion had a median diameter of 0.40 μm, maximum particle diameter of 2.0 μm or less and variation coefficient of 20% for mean particle diameter. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove dusts and so forth, and used for the preparation of the coating solution described above.

[0339] <<Preparation of Coating Solution for Lower Protective Layer>>

[0340] In an amount of 900 g of a polymer latex solution containing copolymer of methyl acrylate/methyl methacrylate=70/30 (weight ratio, mean particle diameter: 110 nm, weight average molecular weight: 800,000, glass transition temperature of copolymer: 30° C., solid content: 28.0 weight %, containing 100 ppm of Compound A) was added with water, 0.2 g of Compound E and 35.0 g of polyvinyl alcohol (PVA-235, Kuraray Co., Ltd.) and further added with water to form a coating solution (containing 0.5 weight % of methanol solvent). After the preparation, the solution was degassed under reduced pressure of 0.47 atm for 60 minutes. The coating solution showed pH of 5.2 and viscosity of 35 mPa·s at 25° C.

[0341] <<Preparation of Coating Solution for Upper Protective Layer>>

[0342] In an amount of 900 g of a polymer latex solution containing copolymer of methyl acrylate/methyl methacrylate=70/30 (weight ratio, mean particle diameter: 110 nm, weight average molecular weight: 800,000, glass transition temperature of copolymer: 30° C., solid content: 28.0 weight %, containing 100 ppm of Compound A) was added with 10.0 g of 30 weight % solution of carnauba wax (Cellosol 524, silicone content: less than 5 ppm, Chukyo Yushi Co., Ltd.), 0.3 g of Compound C, 1.2 g of Compound E, 25.0 g of Compound F, 6.0 g of Compound H, 5.0 g of matting agent (polystyrene particles, mean particle diameter: 7 μm, variation coefficient of 8% for mean particle diameter) and 40.0 g of polyvinyl alcohol (PVA-235, Kuraray Co., Ltd.), and further added with water to form a coating solution (containing 1.5 weight % of methanol solvent). After the preparation, the solution was degassed under reduced pressure of 0.47 atm for 60 minutes. The coating solution showed pH of 2.4 and viscosity of 35 mPa·s at 25° C.

[0343] <<Preparation of Photothermographic Material>>

[0344] On undercoat layers of a PET support coated with the undercoat layers as described in Example 1, the aforementioned coating solution for image-forming layer, coating solution for lower protective layer and coating solution for upper protective layer were simultaneously coated as stacked layers in this order from the support by the slide bead method disclosed in JP-A-2000-2964, FIG. 1, so that the coated silver amount in the image-forming layer should become 1.5 g/m2, the coated solid content of the polymer latex in the lower protective layer should become 1.0 g/m2, and the coated solid content of the polymer latex in the upper protective layer should become 1.3 g/m2.

[0345] As for drying conditions after the coating, the layers were dried in a first drying zone (low wind velocity drying region) at a dry-bulb temperature of 70-75° C., dew point of 9-23° C., wind velocity of 8-10 m/second at the support surface and liquid film surface temperature of 35-40° C., and in a second drying zone (high wind velocity drying region) at a dry-bulb temperature of 65-70° C., dew point of 20-23° C. and wind velocity of 20-25 m/second at the support surface. The drying was performed with the residence time in the first drying zone corresponding to ⅔ of the period of the constant ratio drying in this zone, and thereafter the material was transferred to the second drying zone and dried. The first drying zone was a horizontal drying zone (the support was at an angle of 1.5-3° to the horizontal direction of the coating machine). The coating speed was 60 m/minute. After the drying, the material was rolled up under the conditions of a temperature of 25±5° C. and relative humidity of 45±10%. The material was rolled up in such a rolled shape that the image-forming layer side should be exposed to the outside so as to conform to the subsequent processing (image-forming layer outside roll). The humidity in the package of the photothermographic material was 20-40% of relative humidity (measured at 25° C.). The obtained photothermographic material showed a film surface pH of 5.0 and Beck's smoothness of 5000 seconds for the image-forming layer side. The opposite surface showed a film surface pH of 5.9 and Beck's smoothness of 500 seconds.

[0346] Samples were prepared and evaluated in the same manner as in Example 1 by using the same silver halide emulsions as Example 1, except that Compound XX-2 or XX-3 was used instead of Compound XX-1. As a result, the samples having the characteristics of the present invention showed good performance as in Example 1.

Example 3

[0347] Samples were prepared in the same manner as in Examples 1 and 2 except that the base described below was used instead of the base used in Examples 1 and 2, and subjected to heat development in the same manner as in Example 1. As a result, the photothermographic materials of the present invention substantially reproduced the results obtained in Examples 1 and 2, and thus the advantages of the present invention were clearly demonstrated.

[0348] <<Preparation of Polyethylene Terephthalate (PET) Support with Back Layers and Undercoat Layers>>

[0349] (1) Preparation of PET Support

[0350] Polyethylene terephthalate having IV (intrinsic viscosity) of 0.66 (measured in phenol/tetrachloroethane=6/4 (weight ratio) at 25° C.) was obtained in a conventional manner by using terephthalic acid and ethylene glycol. The product was pelletized, dried at 130° C. for 4 hours, melted at 300° C., then extruded from a T-die and rapidly cooled to form an unstretched film having such a thickness that the thickness should become 120 μm after thermal fixation.

[0351] The film was stretched along the longitudinal direction by 3.3 times using rollers of different peripheral speeds, and then stretched along the transverse direction by 4.5 times using a tenter. These operations were performed at temperatures of 110° C. and 130° C., respectively. Then, the film was subjected to thermal fixation at 240° C. for 20 seconds, and relaxed by 4% along the transverse direction at the same temperature. Then, the chuck of the tenter was released, the both edges of the film were knurled, and the film was rolled up at 4.8 kg/cm2. Thus, a roll of a PET support having a width of 1.4 m, length of 3500 m, and thickness of 120 μm was obtained.

[0352] (2) Preparation of Undercoat Layers and Back Layers

[0353] Coating solutions S-A to S-C were prepared, and Coating solutions S-C and S-A were coated on the image-forming layer coating side of the support in that order from the support in amounts of 13.8 ml/m2 and 6.2 ml/m2, respectively. Further, Coating solutions S-A and S-B were coated on the back layer coating side in that order from the support in amounts of 6.2 ml/m2and 13.8 ml/m2, respectively. The coated layers were dried at 125° C. for 30 seconds, 150° C. for 30 seconds, and 185° C. for 30 seconds. Both surfaces of the PET support were subjected to a corona discharge treatment of 0.375 kV-A-minute/m2.

10(i) Coating solution S-ALatex A mentioned above280gKOH0.5gPolystyrene microparticles0.03g(mean particle diameter: 2 μm,variation coefficient of 7%for mean particle diameter)2,4-Dichloro-6-hydroxy-s-triazine1.8gCompound Bc-C0.06gDistilled waterAmount givingtotal weight of1000g(ii) Coating solution S-CPesresin A52046g(30 weight % aqueous dispersionTakamatsu Yushi Co., Ltd.)Alkali-treated gelatin4.44g(molecular weight: about 10000,Ca2+ content: 30 ppm)Deionized gelatin0.84g(Ca2+ content: 0.6 ppm)Compound Bc-A0.02gDye Bc-AAmount givingoptical densityof 1.3 at 783 nm,Polyoxyethylene phenyl ether1.7gWater-soluble melamine compound15g(Sumitex Resin M-3, SumitomoChemical Co., Ltd., 8 weight %aqueous solution)Aqueous dispersion of Sb-doped81.5gSbO2 acicular grains (FS-10D,Ishihara Sangyo Kaisha, Ltd.)Polystyrene microparticles0.03g(mean diameter: 2.0 μm,variation coefficient of 7%for mean particle diameter)Distilled waterAmount givingtotal weight of1000g(iii) Coating solution S-BChemipearl S12073.1g(27 weight % aqueous dispersionMitsui Chemical Co., Ltd.)Pesresin A615G78.9g(25 weight % aqueous dispersionTakamatsu Yushi Co., Ltd.)Compound Bc-B2.7gCompound Bc-C0.3gCompound Bc-D0.25gWater-soluble epoxy compound3.4mg/m2(Denacol EX-521, Nagase Kasei Co., Ltd.)Polymethyl methacrylate7.7g(10 weight % aqueous dispersion,mean particle diameter: 5.0 μm,variation coefficient of 7%for mean particle diameter)Distilled waterAmount givingtotal weight of1000g

[0354] (3) Heat Treatment During Transportation

[0355] (3-1) Heat Treatment

[0356] The PET support with back layers and undercoat layers prepared as described above was introduced into a heat treatment zone having a total length of 200 m set at 160° C., and transported at a tension of 2 kg/cm2 and a transportation speed of 20 m/minute.

[0357] (3-2) Post-Heat Treatment

[0358] Following the aforementioned heat treatment, the support was subjected to a post-heat treatment by passing it through a zone at 40° C. for 15 seconds, and rolled up. The rolling up tension for this operation was 10 kg/cm2.

Example 4

[0359] (Preparation of Undercoated Support for Photographic Use)

[0360] Both surfaces of a PET film prepared in the same manner as in Example 1 were subjected to a corona discharge treatment of 8 W/m2·minute, and Coating solution for undercoat layer a-1 mentioned below was coated on one of the surfaces in an amount giving a dry thickness of 0.8 μm and dried to obtain Undercoat layer A-1. Further, Coating solution for undercoat layer b-1 mentioned below, which contained an antistatic agent, was coated on the opposite surface in an amount giving a dry thickness of 0.8 μm and dried to obtain Undercoat layer B-1.

11<<Coating solution for undercoat layer a-1>>Latex solution of copolymer of butyl270gacrylate/tert-butyl acrylate/styrene/2-hydroxyethyl acrylate =30/20/25/25 (weight %,solid content: 30%)(C-1) mentioned below0.6gHexamethylene-1,6-bis (ethyleneurea)0.8gPolystyrene particles0.05g(average particle size: 3 μm)Colloidal silica0.1gThe components were filled up to 1 L with water.<<Coating solution for undercoat layer b-1>>SnO2/Sb (weight ratio = 9:1,Amount giving(average particle size: 0.18 μm)coated amount of200mg/m2Latex of solution of copolymer of270gbutyl acrylate/styrene/glycidylacrylate = 30/20/40 (weight %,solid content: 30%)(C-1)0.6gHexamethylene-1,6-bis (ethyleneurea)0.8gThe components were filled up to 1 L with water.

[0361] Subsequently, the upper surfaces of Undercoat layer A-1 and Undercoat layer B-1 were subjected to a corona discharge treatment of 8 W/m2·minute, and Coating solution for upper undercoat layer a-2 mentioned below was coated on Undercoat layer A-1 in an amount giving a dry thickness of 0.9 μm and dried to provide Upper undercoat layer A-2. Further, Coating solution for upper undercoat layer b-2 mentioned below was coated on Undercoat layer B-1 in an amount giving a dry thickness of 0.2 μm and dried to provide Upper undercoat layer B-2 having antistatic property.

12<<Coating solution for upper undercoat layer a-2>>GelatinAmount givingcoated amountof 3.6 mg/m2(C-1)0.2 g(C-2) mentioned below0.2 g(C-3) mentioned below0.1 gSilica particles0.1 g(average particle size: 3 μm)The components were filled up to 1 L with water.<<Coating solution for upper undercoat layer b-2>>(C-4) mentioned below60.0 gLatex solution comprising (C-5)80.0 gmentioned below as component(solid content: 30%)Ammonium sulfate0.5 g(C-6) mentioned below12 gPolyethylene glycol6 g(weight average molecular weight: 600)The components were filled up to 1 L with water.(C-1)

133

(C-2)

134

(C-3)

135

(C-4)

136

x:y = 75:25 (weight ratio) (C-5)

137

138

p:q:r:s:t = 40:5:10:5:40 (weight ratio) (Mn means number average molecular weight) (C-6) Mixture of following three kinds of compounds:

139

140

141

[0362] (Heat Treatment of Support)

[0363] The aforementioned undercoated support was subjected to a heat treatment in the same manner as in Example 1.

[0364] (Preparation of Silver Halide Emulsions A′ to K′)

[0365] In the preparation of Silver halide emulsions A to K in Example 1, after the addition by the control double jet method while maintaining pAg at 7.7 over 33 minutes, 5×10−4 mol/L of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added and pH and pAg were adjusted to 8 and 6.5, respectively, with NaOH to perform reduction sensitization. Then, coagulation precipitation was attained by using a coagulant, then after desalting, 0.1 g of phenoxyethanol was added and pH and pAg were adjusted to 5.9 and 7.5, respectively, to obtain each of Silver halide emulsions A′ to K′.

[0366] The grains of the obtained Silver halide emulsions A′ to K′ had a mean grain size, variation coefficient for projected area, [100] face ratio and twin crystal grain ratio similar to those of Silver halide emulsions A to K, respectively.

[0367] (Preparation of Sodium Behenate Solution)

[0368] In an amount of 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved in 945 mL of pure water at 90° C. Then, the solution was added with 98 mL of 1.5 mol/L sodium hydroxide aqueous solution with stirring at high speed. Subsequently, the solution was added with 0.93 mL of concentrated nitric acid, then cooled to 55° C. and stirred for 30 minutes to obtain a sodium behenate solution.

[0369] (Preparation of Preform Emulsions of Silver Behenate and Silver Halide Emulsions A′ to K′)

[0370] The aforementioned sodium behenate solution was added with 15.1 g of each of Silver halide emulsions A′ to K′ mentioned above, adjusted to pH 8.1 with a sodium hydroxide solution, then added with 147 mL of 1 M silver nitrate solution over 7 minutes, and stirred for 20 minutes, and water-soluble salts were removed by ultrafiltration. The obtained silver behenate was in the form of grains having a mean grain size of 0.8 um and monodispersion degree of 8%. After flocculates of the dispersion was formed, water was removed and the residue was subjected to 6 times of washing with water and removal of water and dried to obtain a preform emulsion.

[0371] (Preparation of Photosensitive Emulsion)

[0372] The obtained each preform emulsion was divided, and one portion was gradually added with 544 g of a solution of polyvinyl butyral (average molecular weight: 3,000) in methyl ethyl ketone (17 weight %) and 107 g of toluene, mixed and then dispersed in a media dispersing machine utilizing a bead mill containing ZrO2 beads having a size of 0.5 mm at 4000 psi and 30° C. for 10 minutes to prepare a photosensitive emulsion.

[0373] The both surfaces of the aforementioned support were simultaneously coated with the following layers to prepare a sample. Each layer was dried at 60° C. for 15 minutes.

[0374] (Coating of Back Surface Side)

[0375] A solution having the following composition was applied on Undercoat layer B-2 of the support.

13Cellulose acetate butyrate15mL/m2(10% methyl ethyl ketone solution)Dye Bc-B mentioned below7mg/m2Dye Bc-C mentioned below7mg/m2Matting agent90mg/m2(monodispersed silica,monodispersion degree: 15%,mean grain size: 8 μm)Fluorinated surfactant50mg/m2(C8F17(CH2CH2O)12C8F17)Fluorinated surfactant10mg/m2(C8F17—C6H4—SO3Na)Dye Bc-B

142

Dye Bc-C

143

[0376] (Coating of Image-Forming Layer Surface Side)

[0377] Photosensitive Layer 1:

[0378] A solution having the following composition was coated on Undercoat layer A-2 of the support in such an amount that the coated silver amount should become 2.4 g/m2.

14Photosensitive emulsion mentioned above240gSensitizing dye B mentioned below1.7mL(0.1% methanol solution)Pyridinium bromide perbromide3mL(6% methanol solution)Calcium bromide1.7mL(0.1% methanol solution)Oxidizing agent mentioned below1.2mL(10% methanol solution)2-(4-Chlorobenzoyl) benzoic acid9.2mL(12% methanol solution)2-Mercaptobenzimidazole11mL(1% methanol solution)Ttribromomethylsulfoquinoline17mL(5% methanol solution)Hydrazine derivative X-3 mentioned below0.4gContrast accelerator P mentioned below0.3gPhthalazine0.6g4-Methylphthalic acid0.25gTetrachlorophthalic acid0.2gCalcium carbonate0.1g(mean particle size: 3 μm)1,1-Bis(2-hydroxy-3,5-dimethylphenyl)-2-20.5mLmethylpropane (20% methanol solution)Isocyanate compound0.5g(Desmodur N3300, Mobay Chemical Co.)Sensitizing dye B

144

Oxidizing agent

145

Hydrazine derivative X-3

146

Contrast accelerator P

147

[0379] Surface Protective Layer:

[0380] A solution having the following composition was coated at the same time of the coating of the image-forming layer thereon.

15Acetone5mL/m2Cellulose acetate butyrate2.3g/m2in methyl ethyl ketoneMethanol7mL/m2Phthalazine250mg/m2Matting agent5mg/m2(monodispersed silica,monodispersion degree: 10%,mean grain size: 4 μm)CH2═CHSO2CH2CH2OCH2CH2SO2CH═CH235mg/m2Fluorinated surfactant10mg/m2(C12F25(CH2CH2O)10C12F25)Fluorinated surfactant10mg/m2(C8F17—C6H4—SO3Na)

[0381] The binder was removed from the samples after the coating layers were formed, and they were observed by electron microscopy according to the replica method. As a result, the organic acid silver salt grains comprises tabular grains having a long axis length of 0.5±0.05 μm, short axis length of 0.4±0.05 um and thickness of 0.01 μm in a ratio of 90% with respect to the total organic acid silver salt grains, and had a monodispersion degree of 5%.

[0382] The samples were prepared by the different coating methods and evaluated. As a result, the samples having the characteristic of the present invention showed good performance as in Example 1.

Example 5

[0383] Samples were prepared in the same manner as in Examples 1-3 except that an equimolar amount of carboxymethyltrimethylthiourea was added instead of the triethylthiourea and 20 μmol of bis(gold(I) 1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) tetrafluoroborate was added in the preparation of silver halide emulsions in Examples 1 to 3, and subjected to heat development in the same manner as in Example 1. As a result, the photothermographic materials of the present invention substantially reproduced the results of Examples 1 to 3, and thus the advantages of the present invention were clearly demonstrated.

Example 6

[0384] The samples prepared in Examples 1 to 5 were exposed by using a cylinder external surface scanning type multichannel exposure apparatus (provided with 30 of 50 mW semiconductor laser heads, laser energy density on the photothermographic material surface: 75 μJ/cm2), and subjected to heat development in the same manner as in Example 1. As a result, the photothermographic materials of the present invention substantially reproduced the results of Examples 1 to 5, and thus it was confirmed that image formation could be effectively attained with the photothermographic materials of the present invention by the method of Example 6.

Example 7

[0385] Samples were prepared in the same manner as in Examples 1 to 5 except that, instead of Sensitizing dye A or Sensitizing dye B, a mixture of Sensitizing dye C and Sensitizing dye D mentioned below at a mixing ratio in mole of 1:1 was added in the same molar amount (as the total amount of Sensitizing dye C and Sensitizing dye D) as Sensitizing dye A in the preparation of silver halide emulsions in Examples 1 to 5, and the samples were evaluated in the same manner as in Example 1 except that an interference filter having a peak at 633 nm was used instead of the interference filter having a peak at 785 nm, and a laser having an output wavelength of 633 nm was used instead of the laser having an output wavelength of 783 nm. As a result, the photothermographic materials of the present invention showed results substantially the same as the results of Examples 1 to 5, and thus the advantages of the present invention were clearly demonstrated.

148

Example 8

[0386] The samples prepared in Examples 1 to 7 were subjected to a heat development with a development time of 20 seconds by using DRY FILM PROCESSOR FDS-6100× produced by Fuji Photo Film Co., Ltd., and similar evaluation was performed. As a result, results similar to those of Examples 1 to 7 were obtained, and thus the advantages of the present invention were clearly demonstrated.

Photothermographic material

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