Abstract:
An object of the present invention is to provide: a polyvinyl acetal resin for a heat-developable photosensitive material capable of preventing skinning in the coating process of the photosensitive layer of the heat-developable photosensitive material, preventing deterioration of image characteristics and coloration of the coating solution, and suppressing the occurrence of odor at the time of producing the heat-developable photosensitive material and heat development. The present invention provides a polyvinyl acetal resin for a heat-developable photosensitive material used for a photosensitive layer of the heat-developable photosensitive material, which has a residual acetyl group content of 25 mol % or less, residual hydroxyl group content of 17-35 mol %, polymerization degree of 200 to 3,000, which is obtained by an acetalization of a polyvinyl alcohol mixture containing polyvinyl alcohol resins having different polymerization degrees, the content of the polyvinyl alcohol having a polymerization degree of 600 or less being 50 wt % or higher in the polyvinyl alcohol mixture.

Description:
TECHNICAL FIELD 
       [0001]    The present invention relates to a polyvinyl acetal resin for a heat-developable photosensitive material capable of preventing skinning in the coating process of the photosensitive layer of the heat-developable photosensitive material, preventing deterioration of image characteristics and coloration of the coating solution, and suppressing the occurrence of odor at the time of producing the heat-developable photosensitive material and heat development. 
       BACKGROUND ART 
       [0002]    By the photo excellent properties, the silver halide light-sensitive material has been used extensively heretofore, have been utilized extensively in the imaging arts as a material of high quality. 
         [0003]    However, the silver halide light-sensitive material of the conventional, there is problems in addition to development and fixing process are complex, and for discharging the chemical waste in a large amount, because the process is wet. 
         [0004]    In contrast, heat-developable photosensitive material capable of performing the heat treatment the development process have been developed and are put to practical use. 
         [0005]    Heat-developable photosensitive material is made of a laminate of photosensitive silver layer that consist from salt of fatty acids, organic reducing agent, small amounts of silver halide dispersed in a binder resin, and support plate such as a paper or plastic film or metal foil or glass plate. 
         [0006]    On the other hand, polymethyl methacrylate resins and polyvinylacetal resins, cellulose acetate resins, polyvinyl acetate resins, cellulose acetate propionate resin, cellulose acetate butyrate and polyvinyl butyral resin, having the excellent film forming properties are the used for the photosensitive layers of the heat developable photosensitive material. Among them, a polyvinyl acetal resin is used as the best. 
         [0007]    These binder resins are generally used a solvent casting method. 
         [0008]    The resin was dissolved into the solvent such as MEK and acetone, alcohol, toluene having relatively low boiling point. And cast onto a support, and dried. It is described in many references. 
         [0009]    The improvement of productivity of the film forming is required on the solvent casting method as described above. 
         [0010]    Reducing the time to the step of release of formed film from step, of resin solution casting onto a support is important. However, the phenomenon of skinning occurs in the process of drying the resin solution, to get the resin film. Skinning is a phenomenon that the casting film surface is solidified by drying, the skin prevents of the evaporation solvent of inside. That Is significantly occurs when we use low-boiling temperature solvents. 
         [0011]    When the skinning occurs, the problem that the image characteristics are deteriorated, because the silver particle density is lowered, had occurred. 
         [0012]    For example, Patent Document 2, a technique that preventing skinning to improving coating properties, the skinning layer is prevent the formation by using a solvent of poor solvent for the binder. 
         [0013]    However, a new problem arose that the dispersibility of the silver particles becomes worse extremely, when the poor solvent used in the silver halide light-sensitive material. 
         [0014]    Further, Patent Document 3, a method of combining the three processes has been disclosed. 
         [0015]    The method comprises the steps of first, casting the resin solution onto a support, the second, applying the vacuum pressure to the support to enable casting film adhere to the support, the third, feeding the anti-skinning solution to the outlet of the resin solution. 
         [0016]    It is possible to prevent the adhesion to the film or the scattering of anti-skinning solution, this method can suppress the skinning. However, there is a problem that adhesion between the support and the casting film become worse in this method. 
       CITATION LIST 
     Patent Literature 
       [0017]    Patent Document 1: Japanese Kokai Publication No. S43-4294 
         [0018]    Patent Document 2: Japanese Kokai Publication No. 2005-104149 
         [0019]    Patent Document 3: Japanese Kokai Publication No. 2011-93106 
       SUMMARY OF THE INVENTION 
     Technical Problem 
       [0020]    As a result of various studies made for solving the aforementioned problems, it has been found that a polyvinyl acetal resin for a heat-developable photosensitive material capable of preventing skinning in the coating process of the photosensitive layer of the heat-developable photosensitive material, preventing deterioration of image characteristics and coloration of the coating solution, and suppressing the occurrence of odor at the time of producing the heat-developable photosensitive material and heat development, and thus, the present invention has been accomplished. 
       Solution to Problem 
       [0021]    The present invention provides a polyvinyl acetal resin for a heat-developable photosensitive material used for a photosensitive layer of the heat-developable photosensitive material, which has a residual acetyl group content of 25 mol % or less, residual hydroxyl group content of 17-35 mol %, polymerization degree of 200 to 3,000, which is obtained by an acetalization of a polyvinyl alcohol mixture containing polyvinyl alcohol resins having different polymerization degrees, the content of the polyvinyl alcohol having a polymerization degree of 600 or less being 50 wt % or higher in the polyvinyl alcohol mixture. 
         [0022]    Below, the present invention will be described in detail. 
         [0023]    A result of extensive studies, the present inventors have found that the following two points were important. They were the use of polyvinyl alcohol that is material of polyvinylacetal resins having different degree of polymerization, and the range of polymerization degree and residual acetyl group content and amount of residual hydroxyl groups of the polyvinylacetal resin. Therefore it found that it was possible to prevent skinning in the coating process, so they have completed the present invention. 
         [0024]    The polyvinylacetal resin of the present invention for heat-developable photosensitive material, the lower limit of the polymerization degree is 200, and, upper limit of polymerization is 3000. 
         [0025]    By the above-mentioned range of polymerization degree, it is possible to have an excellent dispersibility of the silver salt, the coating film strength, the coating property. Further, considering the dispersion of the silver salt, the strength of the coating, the balance of the coating, a preferred lower limit of the polymerization degree is 300, a preferred upper limit of the polymerization degree is 1000. 
         [0026]    The polyvinylacetal resin of the present invention for heat-developable photosensitive material, preferred lower limit of acetalization degree is 40 mol %, and a preferred upper limit is 78 mol %. 
         [0027]    If it is less than 40 mol %, it may not be used as a binder resin of the photosensitive layer of the heat developing photosensitive material, because it becomes insoluble in organic solvents. If the acetal group exceed 78 mol %, the strength of the coating film may decrease toughness, because the polyvinylacetal resin&#39;s residual hydroxyl group amount is less. A more preferred lower limit of the acetalization degree is 65 mol %, more preferred upper limit is 80 mol %. As used herein, the acetalization degree (mol %) is calculated by using a method for evaluating an amount of two hydroxyl groups, since the acetal group of the polyvinyl acetal resin is formed from two hydroxyl groups. 
         [0028]    The polyvinyl acetal resin of the invention for heat-developable photosensitive material, the upper limit of the residual acetyl group content is 25 mol %. If it exceeds 25 mol %, blocking occurs in the synthesis step of the polyvinylacetal. The preferred upper limit is 15 mol %. In addition, the more preferred lower limit of the residual acetyl group content is 0 mol %. 
         [0029]    The lower limit of the residual hydroxyl group content of polyvinyl acetal resin of for the heat-developable photosensitive material is 17 mol % and the upper limit is 35 mol % in the present invention. If it is less than 17 mol %, photographic sensitivity becomes worse, because dispersibility of the silver salt is bad. 
         [0030]    If it is more than 35 mol %, the storage stability and photographic sensitivity of heat-developable photosensitive material becomes worse, because of fogging caused by moisture absorption. The preferred lower limit of the hydroxyl group content is 20 mol %, the preferred upper limit is 33 mol %. 
         [0031]    The polyvinylacetal resin for heat-developable photosensitive material of the present invention is obtained by an acetalization of a polyvinyl alcohol mixture containing polyvinyl alcohol resins having different polymerization degrees, and the content of the polyvinyl alcohol having a polymerization degree of 600 or less is 50 wt % or higher in the polyvinyl alcohol mixture. 
         [0032]    Conventionally, as methods of preventing skinning of the coating film, a method of using a plasticizer or surfactant, and method of using a high boiling solvent which is difficult to dry at drying temperature were used other than a method of using poor solvents as described above. However, there were problems in which the adhesion of each layer was reduced in producing heat-developable photosensitive material in these methods. 
         [0033]    In contrast, the present invention is effectively possible to prevent the occurrence of skinning, due to using the polyvinyl alcohols having different polymerization degree of polyvinyl alcohol as a raw material, and defining the ratio of the polyvinyl alcohol having a predetermined polymerization degree. 
         [0034]    The polyvinylacetal resin for heat-developable photosensitive material of the present invention is obtained by an acetalization of a polyvinyl alcohol mixture containing polyvinyl alcohol resins having different polymerization degrees. 
         [0035]    In order to use polyvinyl alcohol resins having different polymerization degree in this manner, it is possible to obtain two advantages. 
         [0036]    The first advantage is to increase the viscosity of the emulsion slurry by using the high polymerization polymer. Another advantage is to improve the dispersion of the silver halide by low polymerization polymer. 
         [0037]    The “polyvinyl alcohol resins” is not limited to the case of 2 polyvinyl alcohol resins; it is also intended to include the case of 3 or more polyvinyl alcohol resins. 
         [0038]    In the present invention, the content of the polyvinyl alcohol having a polymerization degree of 600 or less is 50 wt % or higher in the polyvinyl alcohol mixture. As a result, it is possible to effectively prevent the occurrence of skinning in the coating step. The content of the polyvinyl alcohol having a polymerization degree of 600 or less is preferably 60 wt % or more. The polyvinyl alcohol having a polymerization degree of 600 or less preferably has polymerization degree of 200 to 600. 
         [0039]    In the polyvinyl alcohol mixture, a polyvinyl alcohol other than the polyvinyl alcohol having a polymerization degree of 600 or less preferably has polymerization degree of 800-3000. Thus, it is possible to reduce the total amount of the binder resin to be added to the slurry because it is easy to increase the viscosity of the silver chloride slurry. Further, in the polyvinyl alcohol mixture, the difference of polymerization degree is preferably 1100 to 2200. Thus, it can be compatible for both coating properties and dispersibility, the drying of the slurry. It should be noted that the difference of the polymerization degree is the difference of the lowest polymerization degree and the highest polymerization degree. 
         [0040]    The preferred lower limit of the saponification degree of the polyvinyl alcohol in polyvinyl alcohol mixture is 75 mol %, the preferred upper limit is 100 mol %. If the saponification is less than 75 mol %, it may not obtain a uniform composition, and therefore the polyvinylacetal resin becomes its particles coalesce in the synthesis process. 
         [0041]    It is desirable that the residue of halogen ion and aldehyde is removed by water washing the heat-developable light-sensitive material of the present invention. Because the residual aldehyde is cause of the odor at the development and the residual halogen ion inhibits the development property. 
         [0042]    On this purpose, it is good that the particle size of polyvinylacetal resin is as small as possible. So it is easy to remove the impurities by water washing. In order to control the polyvinylacetal particle size, it is preferably the polyvinyl alcohol resin has high saponification degree as possible. 
         [0043]    In the polyvinyl acetal resin for the heat-developable photosensitive material of the present invention, it is preferable that the resin has the 0.1 to 5 mol % at least one functional group of the functional group selected from the functional group shown in the following general formulas (1) to (6) in the side chain. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0044]    In the formulas, M represents K H, Li, or Na, R represents an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. 
         [0045]    Since the functional groups have a hydrophilic property, they are assumed that dispersion of the silver salt in the heat-developable photosensitive material is improved, excellent sharpness of the image and tone are obtained. Further, it is possible in the case of using the heat-developable photosensitive material, thereby preventing deterioration of photo characteristics and coloration of the coating solution. 
         [0046]    Examples of the functional group represented by the above general formula (1), for example, it is carboxyl group. 
         [0047]    Examples of the alkyl group include those having 1 to 10 carbon atoms, concretely that is methyl group, ethyl group, isopropyl group, butyl group, t-butyl group, a cyclohexyl group. 
         [0048]    The tertiary amine groups above, for example that is, trimethylamine, triethylamine, triethanolamine, tripropylamine, tributylamine. 
         [0049]    A preferred lower limit of the content of the functional groups is 0.1 mol %, the upper limit is preferably 5 mol %. When it is less than 0.1 mol %, the effect of introducing the functional group, i.e., may not be obtained the effect of improving dispersibility of the silver salt of reducible non-photosensitive. When it is more than 5 mol %, the effect of improving dispersibility of silver salt capable of being reduced non-photosensitive not only saturated, solubility in solvents is deteriorated. 
         [0050]    In the invention, the polyvinylacetal resin for the heat-developable photosensitive material is included the content of each alkali metal, alkaline earth metal, halide ions, sulfate ions and nitrate ions preferably is 100 ppm or less. In particular, when the content of the halogen ion is more than 100 ppm, storage stability of the coating solution is deteriorated. Also, sometimes the storage stability of the photosensitive material is deteriorated, causing fogging. How to be the upper limit of the alkali metal to 100 ppm, alkaline earth metal, halide ions, sulfate ions and nitrate ions, for example, a method of using the halogen-free catalyst used in the acetalization reaction. Then, if the halogen catalyst is used, the resin is purified by washing operation with a mixed solution such as water, water/alcohol, is removed to the specified amount or less. The more preferred upper limit is 50 ppm. 
         [0051]    In the invention, the polyvinylacetal resin for the heat-developable photosensitive material is included the amount of residual alkaline material for resin preferably is 0.01 wt % or less. 
         [0052]    In particular, if the content of the alkali substance is more than 0.01 wt %, storage stability of the coating solution and storage stability of film is deteriorated. How to be the upper limit of the content of the alkaline residue material to 0.01 wt %, for example, a method in which the excess alkaline substance are washed with mixed solution of water or water/alcohol after neutralization in the acetalization reaction and a method of using the volatile alkaline neutralizing agent, the alkali material are removed by heating. The more preferred upper limit is 0.005 wt %. 
         [0053]    In the present invention, the preferred upper limit of the water content of the polyvinylacetal resin for the heat-developable photosensitive material is 3.0 wt %. 
         [0054]    If it is more than 3.0 wt %, strength of the coating layer becomes insufficient, since the pot life of heat developing photosensitive materials fall and it reacts a crosslinking agent which has an isocyanate group added for the purpose of strengthening of a coat layer of the heat-developable photosensitive material. The more preferred upper limit is 2.5 wt %. 
         [0055]    In the invention, the preferred upper limit of the content of 2-ethyl-2-hexenal of polyvinylacetal resin for the heat-developable photosensitive material is 60 ppm. For example, the 2-ethyl-2-hexenal, is produced by dehydration after the aldehyde which used during the acetalization of the polyvinyl alcohol resin is combined aldol condensation. It becomes the cause of smell if the 2-ethyl-2-hexena content exceeds above 60 ppm. Because it is volatilized at heat development or the production of the heat-developable photosensitive material, the human senses as smell. 
         [0056]    It is not limited the method in which the content of 2-ethyl-2-hexenal is 60 ppm or less. 
         [0057]    The 2-ethyl-2-hexenal is generated under the condition of high temperature and high alkaline strength in the neutralization process. For example, the method for inhibiting the production of the 2-ethyl-2-hexenal is keeping the temperature not too high in alkaline conditions or neutralization step. Further, there was washing method that 2-ethyl-2-hexenal are washed with distilled water. 
         [0058]    In the method of washing 2-ethyl-2-hexenal with distilled water, if the particle size of polyvinylacetal resin is large, the cleaning efficiency is deteriorated in the cleaning process and it may not be able to sufficiently remove 2-ethyl-2-hexenal. 
         [0059]    In this case, even if a cleaning time is longer, it cannot be cleaned inside of the resin sufficiently, and the content of the 2-ethyl-2-hexenal may not be reduced to 60 ppm or less. Therefore, in order to increase the washing efficiency, it is necessary to reduce the particle size of the polyvinylacetal resin. 
         [0060]    As a method of reducing the particle size of the particles of the polyvinylacetal resin, for example, there are a method of washing only particles of the polyvinylacetal resin capable of passing through #60 mesh sieve before washing, a method of milling the particles of the polyvinylacetal resin by the ball mill to pass through the #60 mesh sieve, in order to increase the production yield, a method of producing particles capable of passing through the #60 mesh sieve by controlling the reaction conditions such as a reaction temperature. Among them, the method of washing only particles of the polyvinylacetal resin capable of passing through #60 mesh sieve is particularly preferred. It means that #60 mesh has the 60 metal wire in one inch around. The #60 mesh have open area size of about 250 microns. 
         [0061]    Here, the particle size of particles capable of passing through the #60 mesh sieve, can be confirmed by optical microscope. The polyvinylacetal resin was grinded and chooses particles of 50 to 100 at random. 
         [0062]    At this time, the preferable lower limit of the ratio of the particles having the particle size of 35 μm or less is 80%. If it is less than 80%, reaction efficiency with alkali neutralization time may be reduced. A more preferred lower limit is 95%. 
         [0063]    Further, in the washing step, in order to prevent contamination of the impurities contained in the wash water, the use of pure water or distilled water is preferable. However, if the particle size of the polyvinylacetal resin for the heat-developable photosensitive material is too small, the resin tends to scatter, the handling property is deteriorated. So, it is possible to perform steps as necessary, to granulate after washing. 
         [0064]    There is no particular limitation as a method of granulating of the polyvinylacetal resin for the heat-developable photosensitive material. For example, there is a method that the particles of the resin are dispersed in water and they are heated, so the particles bonding together, after washing. 
         [0065]    Further, there is a method of pressing the resin at room temperature, heating to the plate, and then grinding to preferred size after drying the resin. 
         [0066]    The method of granulating the polyvinylacetal resin for the heat-developable photosensitive material is not particularly limited, for example, rolling granulation, extrusion granulation, compression granulation, stirring granulation, spray drying method, dissolution coagulation method, are shown. The compression granulation method is the most preferable. 
         [0067]    By granulating the powder of the polyvinylacetal resin for the heat-developable photosensitive material, it becomes dissolving in solvent easily, and handling significantly is improved, because the powder don&#39;t scattered. 
         [0068]    The bulk density of the polyvinylacetal resin for heat-developable photosensitive material is not particularly limited, 0.3 to 0.5 cm 3 /g is preferable, 0.34 to 0.46 cm 3 /g is more preferable. 
         [0069]    The granulated resins made in these ranges have both the solubility in solvent and preferred handling properties. 
         [0070]    The production method of the polyvinylacetal resin for heat-developable photosensitive material of the invention is made by acetalization of polyvinyl alcohol mixture as described above. 
         [0071]    It is not limited to the specific method of the acetalization. For example, there is the acetalization method that adding acid catalyst and aldehyde are added into the aqueous polyvinyl alcohol mixed solution. 
         [0072]    It is not particularly limited for the aldehyde. For example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, amyl aldehyde, hexyl aldehyde, heptyl aldehyde, 2-ethylhexyl aldehyde, cyclohexyl aldehyde, furfural, glyoxal, glutaraldehyde, benzaldehyde, 2-methyl benzaldehyde, 3-methyl benzaldehyde, 4-methyl benzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, and β-phenylpropionaldehyde, are shown. Among these, it is preferred that only butyraldehyde or acetaldehyde is used. Further, it is preferred that combination using of butyraldehyde and acetaldehyde. 
         [0073]    If the butyraldehyde and acetaldehyde are used, the sharpness of the image and the gradation portion become excellent. The dispersion of the silver salt heat-developable photosensitive material is improved, hot-melt ability, cool-solidify ability, etc becomes sharper. Because it makes possible to accurately control the nuclear growth of silver salt. 
         [0074]    The preferred lower limit of the ratio of the portion acetalized with acetaldehyde is 30% of the total acetal group. 
         [0075]    In some cases, if it were less than 30%, the sharpness and resolution of the image becomes insufficient. Since the glass transition temperature of the polyvinyl acetal resin becomes 80° C. or less, nucleation of the photosensitive silver salt of the heat-developable photosensitive material is too proceeds. Further, the dispersibility of the silver salt cannot be obtained sufficiently. The more preferred lower limit is 50%. 
         [0076]    The acid catalyst is not particularly limited, both organic acids and inorganic acids also may be used. 
         [0077]    For example, acetic acid, p-toluene sulfonic acid, nitric acid, sulfuric acid, hydrochloric acid are shown. Further, in order to stop the synthesis reaction, alkali neutralization is carried out. 
         [0078]    For example the alkalis used in the neutralization are shown below, sodium hydroxide, potassium hydroxide, ammonia, sodium acetate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogen carbonate. 
         [0079]    In the above the acetalization, usually, the antioxidant is added in order to prevent oxidation of the resin and prevent oxidation of the aldehyde, also improve the heat resistance. 
         [0080]    However, it is preferable that the polyvinylacetal resin does not contain the antioxidants which are bisphenol-based, a phosphoric acid type, hindered phenol used as the antioxidant usually. 
         [0081]    Sometimes such antioxidants is remaining in the polyvinyl acetal resin, thereby declining the sharpness and causing fog. Because they cause deterioration of the storage stability of the film and deterioration of the storage ability of the coating solution. 
         [0082]    The method of making the polyvinylacetal resin for heat-developable photosensitive material which has functional groups in side chain described above is as follows. For example, a method of copolymerizing the vinyl ester and the monomer having functional group and acetalizating the polyvinyl alcohol resin obtained by saponifying of the copolymer and a method of using the hydroxyl group of the polyvinylacetal resin or a polyvinyl alcohol resin and introducing functional groups are used. The monomer having the functional group is shown as, for example, acrylic acid, maleic acid, itaconic acid. 
         [0083]    In the invention, the polyvinylacetal resin for the heat-developable photosensitive material is preferably carried out the washing step after the acetalization. Thus, in particular, it is possible to reduce the content of 2-ethyl-2-hexenal. The detail of the cleaning step is described above. 
         [0084]    A heat-developable photosensitive material can be prepared by the following procedure. 
         [0085]    First, it is mixed up the polyvinylacetal resin for heat-developable photosensitive material of the invention, an organic silver salt, photosensitive silver halide, silver ion reducing agents, crosslinking agents, solvents and additives. Next, it is coated on support the mixed solution and dried. 
         [0086]    The heat-developable photosensitive material containing organic silver salt, silver ion reducing agent and light-sensitive silver halide in addition to polyvinylacetal resin for the heat developable photosensitive material is also included in the invention. 
         [0087]    In the invention, the preferred lower limit of the content of polyvinylacetal resin for the heat-developable photosensitive material in the photosensitive layer, (heat-developable photosensitive material for polyvinyl acetal resin of the present invention: organic silver salt) weight ratio of the organic silver salt, 1:10, the preferred upper limit is preferably 10:1. 
         [0088]    In less than 1:10, it is not possible to improve the adhesion between the layers constituting the heat-developable photosensitive material. If it is more than 10:1, there is the image becomes blurred. The more preferred lower limit is 1:5, the more preferred upper limit is 5:1. 
         [0089]    In the invention, the preferred lower limit of the content of the polyvinyl acetal resin for the heat-developable photosensitive material in all of the photosensitive layer is 5 wt %, the preferred upper limit is 20 wt %. In this range, the photo quality may be improved, because dispersibility of the silver halide in the slurry becomes good. 
         [0090]    The organic silver salt is a silver salt of white or colorless relatively stable to light. 
         [0091]    When it is heated at 80° C., the photosensitive silver halide reacts with the silver ion reducing agent and it became the silver metal. 
         [0092]    The organic silver salt is not particularly limited. For example, silver salts of organic compounds having a carboxyl group mercapto group, or a thione group, silver benzotriazole are shown. 
         [0093]    Specifically, the silver salt of compound having mercapto group or thione group, silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, silver salt of 2-mercapto-benzimidazole, silver salt of 2-mercapto-5-aminothiazole, silver salts of 1-phenyl-5-phenyl-mercaptotetrathiazole, silver salt of 2-mercapto-benzothiazole, silver salt of thioglycolic acid, silver salt of dithiocarboxylic acid such as silver salt of dithioacetic acid, thioamide silver, silver salt of thiopyridine, silver salt of dithiohydroxybenzol, silver salt of mercaptotriazine, silver salts of mercaptooxadiazole, silver salt of an aliphatic carboxylic acid, Capric acid silver, Lauric acid silver, Myristic acid silver, Palmitic acid silver, Stearic acid silver, Behenic acid silver, Malic acid silver, fumaric acid silver, silver tartrate, Furoin silver, linoleic acid silver, Oleic acid silver, hydroxystearic acid silver, adipic acid silver, sebacic acid silver, malic acid silver, silver acetate, Butyric acid silver, Oxalic acid silver, Aromatic carboxylic acids silver, thiocarboxylic acid silver, Aliphatic carboxylic silver having thioether group, silver salt of tetrazaindene, S-2-amino phenyl silver thiosulfate, including Metal amino alcohols, and organic acid metal chelates are shown. 
         [0094]    The preferred lower limit of the average particle size of the organic silver salt is 0.01 μm. And the preferred upper limit is 10 μm. When it is used that the above range of average particle size of the organic silver salt, dispersibility is good, the high photo density can be obtained. 
         [0095]    The more preferred upper limit is 0.2 μm, and the preferred lower limit 5 μm. 
         [0096]    The photosensitive silver halide is not particularly limited. For example, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, silver iodide salt are shown. In addition, the above-mentioned light-sensitive silver halide are chemically sensitized by sensitizing agent. 
         [0097]    The methods of chemical sensitization of the photosensitive silver halide are not particularly limited. 
         [0098]    For example, sulfur sensitizations, selenium sensitization, tellurium sensitization method, are shown. 
         [0099]    Photosensitive silver halide may be chemically sensitized by the reduction sensitization method, which uses as a noble metal sensitization method using a sensitizer of platinum, palladium, iridium compounds, a sensitizer such as ascorbic acid, thiourea dioxide, etc. possible. 
         [0100]    The photosensitive silver halide is preferably spectrally-sensitized by combination of sensitizing pigment. By combining the sensitizing pigments, it is possible to be spectrally sensitized to the absorption wavelength range of the desired light-sensitive silver halide, depending on the wavelength range of the light source. 
         [0101]    The preferred lower limit of the content of the photosensitive silver halide is 0.0005 parts by weight per 100 parts by weight of the organic silver salt. In addition, the preferred upper limit is 0.2 parts by weight. If it is less than 0.0005 parts by weight, the image after development becomes unclear. 
         [0102]    If it exceeds 0.2 parts by weight, the image after development becomes cloudy. A more preferred lower limit is 0.01 parts by weight. 
         [0103]    The reducing agent is not particularly limited as long as any substance which reduces silver ions into metallic silver. For example, chlorophenols, bisphenols, naphthols, bisnaphthol, polyhydroxybenzenes, dihydroxy naphthols, polyhydroxy naphthols, dihydroxy naphthalenes, polyhydroxy naphthalenes, hydroquinone, hydroquinone monoether, ascorbic acid or ascorbic acid derivative, Reducing saccharide, aromatic amino compounds, hydroxylamines, hydrazines, phenidones, hindered phenols, are shown. Among them, the reducing agent of photodegradable is preferably used. It may also be used reducing agent thermally decomposable. 
         [0104]    Furthermore, it can be used in combination with compounds that promote photodegradation. It can also be used that combination agents to inhibit the reaction with a reducing agent to the silver halide. 
         [0105]    The preferable lower limit of the content of the reducing agent is 0.0001 parts by weight per 100 parts by weight of the organic silver salt. The preferred upper limit is 3.0 parts by weight. 
         [0106]    It is possible by the above-mentioned range, to appropriately reduction of the organic silver salt. 
         [0107]    The more preferred lower limit is 0.01 parts by weight. The upper limit is more preferably 1.0 parts by weight. 
         [0108]    The additive is not limited particularly, for example, the color formulations are shown. 
         [0109]    The color formulation has a function to participate in the redox reaction with reducing agent and the organic silver salt, and the black silver image produced. The color formulation is not particularly limited. For example, imides, naphthol imides, mercaptans, N-(aminomethyl) aryldicarboximides, and blocked pyrazoles, phthalazinone, or phthalazinone derivative, metal salts of phthalazinone derivatives, phthalazine, phthalic acid, and 2,3-naphthalene dicarboxylic acid, or o-phenylene acid derivative, anhydride of phenylene acid derivative, quinazolinediones, benzoxazine, narutokisajin derivative, 2,4-benzoxazin, pyrimidines, tetraazapentalene derivatives are shown. Among these, phthalazine or phthalazine is preferred. 
         [0110]    The support or substrates are not particularly limited. For example, polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, polyolefins such as polyethylene and polypropylene, polyvinylacetals, polyimides, cellulose esters such as nitrocellulose, cellulose diacetate, cellulose triacetate, plastic film made of vinyl chloride resin, chlorinated polypropylene, metal plate or the like made of glass, paper, aluminum are shown. Among these, polyethylene terephthalate is preferred. 
         [0111]    The preferred lower limit of the amount of silver that is applied onto the supporter is 0.1 g per 1 m 2  of support. The upper limit is 5 g. The more preferred lower limit is 0.3 g, and the more preferred upper limit is 3 g. If it is less than 0.1 g, the image density may become low, even if it exceeds 5 g, is not observed improvement in image density. 
         [0112]    In the invention, specific method of manufacturing the heat developable photosensitive material is not limited. Method of making the heat developable photosensitive material may be mentioned the following method. For example, mixing in a ball mill solvent, polyvinylacetal resin, organic silver salt, silver ion reducing agent, photosensitive silver halide, and additives, were dispersed to solution. 
         [0113]    Then, it is coated on a support an organic silver salt, this solution and drying the solvent. 
         [0114]    Note that the photosensitive silver halide, may be formed by the action of light-sensitive silver halide forming component in the organic silver salt and the photosensitive silver halide of a portion of an organic silver salt. 
         [0115]    In the invention, the above reducing agent and the organic silver salt, were mixed in the polyvinylacetal resin for heat-developable photosensitive material in a batch, to form a photosensitive layer further on the support. In addition, the polyvinylacetal resin for the heat-developable photosensitive material and reducing agent and the organic silver salt are mixed separately, thereby forming a photosensitive layer of the two layers can be laminated to each other. 
         [0116]    Furthermore, the photosensitive layer may be formed on both surfaces of the substrate, and also may be formed on only one surface of the support. 
         [0117]    There is no particular limitation for the solvent. In the invention, it is possible to use the solvent which can dissolve the polyvinylacetal resin for the heat-developable photosensitive material. 
         [0118]    Then, having less water content is preferably used. 
         [0119]    For example, specifically, ketones such as diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and esters such as methyl acetate, ethyl acetate, propyl acetate can be used. 
         [0120]    In the case of using ethanol, n-propyl alcohol, isopropyl alcohol, it is preferred that to use the dehydrated grade. 
       Advantageous Effects of Invention 
       [0121]    By the invention, it can be provided the polyvinylacetal resin for a heat-developable photosensitive material and the heat-developable photosensitive material satisfies the following. 
         [0122]    In other words, it can be prevent skinning in coating process of the photosensitive layer of the heat-developable photosensitive material. Then it is possible to prevent the deterioration of the photo characteristics and coloration of the coating solution. 
         [0123]    Further, it is possible to suppress the occurrence of odor at the time of heat development and production of the heat-developable photosensitive material. 
     
    
     DESCRIPTION OF EMBODIMENTS 
       [0124]    And the invention is further illustrated by the following examples, but the present invention is not limited to these examples. 
       Example 1 
       [0125]    50 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 600, and 26 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 800, and 24 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 1700, were dissolved in 700 g of distilled water by heating. 
         [0126]    It was kept at 20° C., then 70% nitric acid 26 g was added, and butylaldehyde 16 g was added further. 
         [0127]    Then it cooled to 10° C. And it was added butylaldehyde 70 g. After the resin was precipitated, and held for 30 minutes, then nitrate 93 g was added and kept for 6 hours the temperature was raised to 35° C. 
         [0128]    After the end of the reaction, for 10 hours flushing with distilled water, and dehydrated the polyvinylbutyral resin after washing. The only particles capable of passing through #60 mesh sieve were dispersed in distilled water and then sodium hydroxide was added to adjust to pH 8. After holding for 6 hours at 50° C., the solution was cooled. 
         [0129]    Then, the solution was washed with running distilled water for 2 hours. Then dehydrated and dried at 40° C. for 12 hours. The polyvinylacetal resin particles were grinded by a mortar, sieved by #60 mesh sieve, and then the only particles capable of passing through the sieve were washed 10 hours with running distilled water. 
         [0130]    The polyvinyl acetal resin was gained after washing, dewatering, and drying. 
         [0131]    Residual acetyl group content of the obtained polyvinyl acetal resin was 1.7 mol %, residual hydroxyl group content was 20 mol %. The ratio of the particles having the particle size of 35 μm or less was 96% in the obtained polyvinyl acetal resin. 
         [0132]    Then, the obtained polyvinyl acetal resin was subjected to granulation treatment by passing through the resin to the two-roll provided with a concave recess on the roll surface. The obtained powder was sieved by 50 mesh sieve and ungranulated powder was removed and then polyvinyl acetal resin powder was obtained. 
       Example 2 
       [0133]    Except for using 35 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 600, and 26 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 400, and 21 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 800, and 18 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 2400, the experiments were conducted in the same manner as in example 1. 
         [0134]    Residual acetyl group content of the obtained polyvinylacetal resin was, 1.1 mol %, residual hydroxyl group content was 28 mol %. 
         [0135]    The ratio of particles having the particle size of 35 μm or less was 98% in the obtained polyvinyl acetal resin. 
         [0136]    The polyvinyl acetal resin powder was obtained by performing granulation in the same manner as in Example 1. 
       Example 3 
       [0137]    95 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 600, and 37 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 1700, (The composition ratio of 600 or less degree of polymerization of the polyvinyl alcohol is 72%), were dissolved in 1600 g of distilled water by heating. 
         [0138]    It was kept at 20° C., then 70% nitric acid 90 g was added, and acetaldehyde 28 g was added further. 
         [0139]    Then it cooled to 13° C., and added butyraldehyde 36 g. After the resin was precipitated, and held for 30 minutes, then kept for 5 hours the temperature was raised to 55° C. 
         [0140]    After the end of the reaction, for 10 hours flushing with distilled water, and dehydrated the polyvinylacetal resin after washing. The only particles capable of passing through #60 mesh sieve were dispersed in distilled water and then sodium bicarbonate was added to adjust to pH 8. After holding for 6 hours at 50° C., the solution was cooled. After cooling, pH was 8. 
         [0141]    Then, the solution was washed with running distilled water for 2 hours. Then dehydrated and dried at 40° C. for 12 hours. The polyvinylacetal resin particles were grinded by a mortar, sieved by #60 mesh sieve, and then the only particles capable of passing through the sieve were washed 10 hours with running distilled water. 
         [0142]    The polyvinyl acetal resin was gained after washing, dewatering, and drying. 
         [0143]    Residual acetyl group content of the obtained polyvinyl acetal resin was 1.8 mol %, residual hydroxyl group content was 26 mol %. 
         [0144]    The acetacetal degree of the obtained polyvinylacetal resin was 37.3 mol % (51.7% per total acetal), butylalization degree was 34.9 mol %. The ratio of the particles having the particle size of 35 μm or less was 95% in the obtained polyvinyl acetal resin. 
         [0145]    The polyvinyl acetal resin powder was obtained by performing granulation in the same manner as in Example 1. 
       Example 4 
       [0146]    Except for using 98 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 400, and 34 g of polyvinyl alcohol in which saponification degree was 98%, polymerization degree was 2400, the experiments were conducted in the same manner as in example 3. 
         [0147]    Residual acetyl group content of the obtained polyvinylacetal resin was 1.3 mol %, residual hydroxyl group content was 23 mol %. 
         [0148]    The ratio of particles having the particle size of 35 μm or less was 98% in the obtained polyvinyl acetal resin 
         [0149]    The polyvinyl acetal resin powder was obtained by performing granulation in the same manner as in Example 1. 
       Comparative Example 1 
       [0150]    Except for using a polyvinyl alcohol resin which polymerization degree was 1700, experiments were conducted in the same manner as in Example 3. 
         [0151]    Residual acetyl group content of the obtained polyvinyl acetal resin was 1.9 mol %, residual hydroxyl group content was 30 mol %. The acetacetal degree of the obtained polyvinylacetal resin was 40.1 mol % (58.9% per total acetal), butylalization degree was 28.0 mol %. After the the reaction and grinding step, except the process of sieving for using #60 mesh sieve, polyvinyl acetal resin powder was obtained in the same manner as in Example 1. 
       Comparative Example 2 
       [0152]    Except for using a polyvinyl alcohol resin in which polymerization degree was 900, experiments were conducted in the same manner as in Example 3. 
         [0153]    Residual acetyl group content of the obtained polyvinyl acetal resin was 1.2 mol %, residual hydroxyl group content was 25 mol %. The acetacetal degree of the obtained polyvinylacetal resin was 50 mol % (79.4% per total acetal), butylalization degree was 13.0 mol %. After the reaction and grinding step, except the process of sieving for using #60 mesh sieve, polyvinyl acetal resin powder was obtained in the same manner as in Example 3. 
         [0154]    (Evaluation) 
         [0155]    For polyvinyl acetal resin powder obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were evaluated by the following methods. The results are shown in Table 1. 
         [0156]    (1) Bulk Specific Gravity 
         [0157]    By the method of JIS K6720, bulk specific gravity of the obtained the polyvinylacetal resin particles was measured. 
         [0158]    (2) Evaluation of Handling Properties of Polyvinylacetal Resin 
         [0159]    14 g of the obtained polyvinylacetal resin was placed in a 100 ml-glass bottle with a lid. 
         [0160]    The resin was dissolved in 56 g of MEK: ethanol (2:8) mixed solution. 
         [0161]    In this case, handling property was evaluated according to the following criteria. 
         [0162]    ◯): Polyvinyl acetal resin powder could be put into a bottle at once. 
         [0163]    X: Polyvinyl acetal resin powder could not be put into a bottle at once. 
         [0164]    It is necessary to introduce it into the bottle several times while dissolving it. 
         [0165]    (3) Evaluation of the Skinning of Coating Layer 
         [0166]    By using the applicator which is set at 10 mil, the resin solution prepared in “(2) Evaluation of handling properties of polyvinylacetal resin” is coated on the PET film and dried 15 minutes at 60° C. oven. Then, the surface condition of the coating film was evaluated. 
         [0167]    ◯): There was no wrinkle and smooth surface was obtained. 
         [0168]    X: There was rough surface, wrinkle, or bubbles due to skinning. 
         [0169]    (4) Content of 2-Ethyl-2-Hexenal 
         [0170]    The content of 2-ethyl-2-hexenal in obtained the polyvinyl acetal resin was measured by Gas chromatography which is connected headspace (Tekmer Dohrmann Co., Ltd.) (GPC: manufactured by Shimadzu Corporation, GC-14, column: TC-WAX PEG using a 0.25 mm×30 m). 
         [0171]    (5) Measurement of the Content of Ions 
         [0172]    The content of sodium ions was evaluated by elemental absorption method. 
         [0173]    In addition, the content of nitrate ions was evaluated by ion chromatography. 
         [0174]    (6) The Evaluation of Coloring of Organic Silver Salt Solution 
         [0175]    The obtained polyvinyl acetal resin powder 5 g, silver behenate 5 g, methyl ethyl ketone 40 g, were mixed in a ball mill for 24 hours. Then, N-lauryl-1-hydroxy-2-naphthamide 0.2 g was added, thereby producing a coating solution by ball-milled again. These solutions were observed color changes under a fluorescent lamp for 3 days at room temperature indoors. 
         [0176]    The evaluation was done by the following criteria. 
         [0177]    ◯): There was no change from white. 
         [0178]    X: Coloration was observed. 
         [0179]    (7) Image Evaluation 
         [0180]    The coating solution prepared in “(6) The evaluation of coloring of organic silver salt solution” was applied on to the polyester substrate and dried so that the after drying thickness was 10 μm. 
         [0181]    On this coated surface, a solution which has the following composition was coated. 
         [0182]    Solution composition: N, N-dimethyl-p-phenylenediamine sulfate 0.5 g, polyvinylpyrrolidone 2 g, methanol 30 mL The dried coating thickness after drying was 1 μm, so photosensitive film was obtained. 
         [0183]    The obtained photosensitive film was exposed for 0.3 seconds at a distance of 20 cm with high pressure mercury such as 250 watt through gradation pattern film. 
         [0184]    Then, it was obtained a pattern image of cyan color by heating 5 seconds using a hot plate of 120° C. 
         [0185]    By exposure to white light pattern image obtained, it was observed a change in the contrast of the pattern image. The evaluation was done by the following criteria. 
         [0186]    ◯): There was no change. 
         [0187]    X: Change was observed. 
         [0188]    (8) Smell 
         [0189]    During producing the photosensitive film at the time of “(7) Image evaluation”, and the heat development, the presence of smell was confirmed by a functional test. Evaluation based on the following criteria. 
         [0190]    ◯: Smell could not be felt. 
         [0191]    X: Smell was felt. 
         [0000]    
       
         
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
             
             
               
                   
                 Polyvinyl alcohol 
                 Polyvinylacetal resin 
               
             
          
           
               
                   
                   
                 Saponification 
                 Mixing 
                   
                 Acetyl group 
                 Hydroxyl group 
                 Acetalization 
                 Bulk specific 
               
               
                   
                 Polymerization 
                 degree 
                 ratio 
                 Polymerization 
                 content 
                 content 
                 degree 
                 gravity 
               
               
                   
                 degree 
                 (mol %) 
                 (Wt %) 
                 degree 
                 (mol %) 
                 (mol %) 
                 (mol %) 
                 (g/cm 3 ) 
               
               
                   
               
               
                 Example 1 
                 600 
                 98 
                 50 
                 900 
                 1.7 
                 20 
                 78.3 
                 0.335 
               
               
                   
                 800 
                 98 
                 26 
               
               
                   
                 1700 
                 98 
                 24 
               
               
                 Example 2 
                 600 
                 98 
                 35 
                 900 
                 1.1 
                 25 
                 70.9 
                 0.375 
               
               
                   
                 400 
                 98 
                 26 
               
               
                   
                 800 
                 98 
                 21 
               
               
                   
                 2400 
                 98 
                 18 
               
               
                 Example 3 
                 600 
                 98 
                 72 
                 900 
                 1.8 
                 26 
                 72.2 
                 0.42 
               
               
                   
                 1700 
                 98 
                 28 
               
               
                 Example 4 
                 400 
                 98 
                 74 
                 900 
                 1.3 
                 24 
                 74.7 
                 0.455 
               
               
                   
                 2400 
                 98 
                 26 
               
               
                 Comparative 
                 1700 
                 98 
                 100 
                 1700 
                 1.9 
                 30 
                 68.1 
                 0.215 
               
               
                 Example 1 
               
               
                 Comparative 
                 900 
                 98 
                 100 
                 900 
                 1.2 
                 25 
                 73.8 
                 0.285 
               
               
                 Example 2 
               
               
                   
               
             
          
           
               
                   
                 Evaluation 
               
             
          
           
               
                   
                   
                   
                   
                 Content of 
                 Content of 
                   
                   
                   
               
               
                   
                   
                   
                   
                 2-ethyl-2-hexenal 
                 ions Na + /NO 3   −   
                   
                 Image 
               
               
                   
                   
                 Handling 
                 Skinning 
                 (ppm) 
                 (ppm) 
                 Coloring 
                 evaluation 
                 Smell 
               
               
                   
                   
               
               
                   
                 Example 1 
                 ◯ 
                 ◯ 
                 28 
                 25/20 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 Example 2 
                 ◯ 
                 ◯ 
                 48 
                 70/75 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 Example 3 
                 ◯ 
                 ◯ 
                 33 
                 55/60 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 Example 4 
                 ◯ 
                 ◯ 
                 50 
                 80/90 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 Comparative 
                 X 
                 X 
                 137 
                 210/220 
                 X 
                 X 
                 X 
               
               
                   
                 Example 1 
               
               
                   
                 Comparative 
                 X 
                 X 
                 140 
                 280/320 
                 X 
                 X 
                 X 
               
               
                   
                 Example 2 
               
               
                   
                   
               
             
          
         
       
     
         [0192]    As shown in Table 1, the obtained polyvinyl acetal resin in Examples 1 to 4, the average of polymerization degree was about 900. Skinning was not observed, the condition of the dry film was good, and the change of the pattern image and the coloring of the coating solution were not observed either. 
         [0193]    In addition, the content of 2-ethyl-2-hexenal is low, bad smell could not be felt during thermal development and photosensitive film production. 
         [0194]    In contrast, polyvinyl acetal resins obtained in Comparative Examples 1 and 2, the skinning state were observed on the surface of dry film. There were changes coloring both of the pattern image and the coating solution. Smell had felt at the development or during producing the photosensitive film.