JP2001166421A - Information recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an information recording material having a small quantity of electric charges and nearly free from plane trouble due to coating. SOLUTION: A fluorine-containing nonionic surfactant, >=1.5×10-5 mol/m2 salt of a polyvalent metal and an anionic surfactant which forms a slightly soluble salt with the polyvalent metal in an aqueous solution are added to a top layer on a substrate on the information recording layer side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an information recording material, and more particularly to a silver halide color photographic material having a small charge amount and improved coating failure, and more particularly to a heat-developable color photographic material.

[0002]

2. Description of the Related Art It is generally known to use a fluorine-containing nonionic surfactant to reduce the charge amount of an information recording material represented by a silver halide photographic light-sensitive material (for example, Japanese Patent Application Laid-Open No. Sho 62-195649). In this case, a fluorine-containing nonionic surfactant is often added to the uppermost layer. On the other hand, in the production of an information recording material, when a hydrophilic layer is simultaneously coated on a support conveyed at a speed of 20 m / min or more, surface defects such as cissing are likely to occur. It is also known to use coating aids in the top layer. In addition, a matting agent, a mordant, an emulsion, or the like may be added to the uppermost layer in order to provide various functions according to the purpose of use of the recording material in addition to the above. As described above, when concentrated addition is performed on the uppermost layer in order to satisfy all the various functions, the materials react with each other, and in the process of applying the information recording layer on the support, a surface failure that affects quality is caused. There is a problem that the yield is remarkably reduced.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an information recording material having a small amount of charge and an improved surface failure due to coating. The purpose of the present invention is to
An object of the present invention is to provide a silver halide photographic light-sensitive material having a small surface failure, particularly a heat-developable color photographic light-sensitive material even in a production method in which two or more layers are simultaneously coated on a support conveyed at 0 m / min or more.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by the following information recording material. (1) A fluorine-containing nonionic surfactant, a polyvalent metal salt of 1.5 × 10 ⁻⁵ mol / m ² or more, and a polyvalent metal and an aqueous solution are formed on the uppermost layer on the information recording layer side on the support. An information recording material comprising an anionic surfactant for forming a hardly soluble salt therein. (2) The information recording material as described in (1) above, wherein a lower layer adjacent to the uppermost layer contains a polyvalent metal salt and an anionic surfactant for forming a sparingly soluble salt with the polyvalent metal. (3) The information recording material as described in (1) or (2) above, wherein the information recording layer is a photosensitive silver halide emulsion layer. (4) On the surface layer on the side of the photosensitive silver halide emulsion layer on the support, a fluorine-containing nonionic surfactant, a polyvalent metal salt of 1.5 × 10 ⁻⁵ mol / m ² or more, and A heat-developable color photographic light-sensitive material comprising an anionic surfactant which forms a sparingly soluble salt in an aqueous solution with a valent metal. (5) The heat-developable color photographic light-sensitive material as described in (4) above, wherein the lower layer adjacent to the uppermost layer contains a polyvalent metal salt and an anionic surfactant for forming a sparingly soluble salt with the polyvalent metal.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the information recording material of the present invention will be described in detail. When two or more layers are simultaneously coated on a support conveyed at a speed of 20 m / min or more, a layer adjacent to the uppermost layer of the information recording material is provided with a polyvalent metal to improve its coatability and add functions. It is effective to include a salt and an anionic surfactant that forms a sparingly soluble salt with the polyvalent metal, but on the other hand, there is a problem that cissing failure is likely to occur. The present invention is particularly effective in solving such a technical problem in the step of applying the information recording material. Further, the present invention can particularly effectively solve the coating failure of the information recording material having the adjacent layer as described in the above items (2) and (5). The fluorine-containing nonionic surfactant which can be used in the information recording material of the present invention is disclosed in British Patent No. 1,330,35.
No. 6, JP-A-49-10722 and JP-A-53-84712.
No. 54-14224, No. 50-11221,
62-195649 and the like. Two or more of these surfactants may be used in combination. Preferred examples of these are shown below.

[0006]

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[0007]

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[0008]

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In the present invention, the amount of the fluorine-containing nonionic surfactant to be used is 0.1 to 1 m 2 per square meter of the information recording material.
It is preferable to use from 0001 to 2.0 g, especially from 0.1 to 2.0 g.
0005-0.1 g is preferred. Examples of the polyvalent metal salt used in the uppermost layer and the adjacent layer include calcium nitrate, magnesium nitrate, barium sulfate, zinc stearate, and the like. Is preferred because it is inert to other materials. The amount of the polyvalent metal salt used for the uppermost layer needs to be 1.5 × 10 ⁻⁵ mol / m ² or more, and 2 × 10 ⁻⁵ mol / m ² to 1 × 10 ⁻⁴ mol. / M ² is preferred. The amount of the polyvalent metal salt used in the layer adjacent to the uppermost layer is preferably 1 × 10 ⁻⁵ mol / m ^{2 to} 5 mol / m ² . When the polyvalent metal salt is calcium nitrate, the amount used is preferably from 1 × 10 ⁻⁵ mol / m ² to 1 × 10 ⁻⁴ mol / m ² .

As the anionic surfactant used in the uppermost layer and the layer adjacent thereto, which forms a sparingly soluble salt with a polyvalent metal in an aqueous solution, for example, an anionic surfactant described in JP-A-6-138623 is used. Can be. The anionic group of the anionic surfactant used in the present invention is a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and the like, and the hydrophobic portion is a hydrocarbon, a partially or fully fluorinated hydrocarbon, and the like. .

The anionic surfactants preferably used in the present invention are represented by Chemical Formulas 4 to 12, but the present invention is not limited to these.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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In the formula 4, R ¹ is a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms or a fluorine-substituted product thereof, such as propyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl group, tridecyl group, octadecyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, heptacosafluorotridecyl group, tritriacontafluoroheptadecyl group and the like. R ² is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, etc.). n is an integer of 1 to 20, particularly preferably 1 to 8. M is a monovalent alkali metal, and Na and K are particularly preferable.

In Chemical Formulas 5 and 6, R ¹ , M and n have the same meanings as in Chemical Formula 1. a represents 0, 1 or 2. m is an integer of 1 to 6, particularly preferably 2 to 4.

In the chemical formulas 7, 8 and 9, R ¹ , M
Has the same meaning as in Chemical Formula 1.

In Chemical Formula 10, R ² and M have the same meanings as in Chemical Formula 1, and m has the same meaning as in Chemical Formula 2.

In the chemical formulas (11) and (12), R ³ is a saturated or unsaturated hydrocarbon group in which the hydrogen moiety having ³ to 22 carbon atoms is fluorinated, preferably 7 to 18 carbon atoms.
(For example, pentadecafluoroheptyl group, heptadecafluorooctyl group, heptacosafluorotridecyl group, tritriacontafluoroheptadecyl group, etc.). R ² and M have the same meanings as in Chemical formula 1, and m has the same meaning as in Chemical formula 2.

Specific examples of particularly preferably used anionic surfactants are as follows. However, the present invention is not specifically limited to these.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The anionic surfactant may be used alone or in combination of two or more. As the information recording material of the present invention, a hydrophilic colloid layer is coated on a support, and any material can be used as long as it can record information. Specifically, heat-sensitive recording materials, pressure-sensitive recording materials, photosensitive materials Materials and image-receiving materials used in diffusion transfer systems. As the light-sensitive material, a silver halide photographic light-sensitive material is typical.
Black-and-white light-sensitive material for lines, black-and-white light-sensitive material for printing), ordinary multilayer color light-sensitive materials (for example, color paper, color reversal film, color negative film, color positive film, color positive paper), film unit for color diffusion transfer, heat Examples include black-and-white and color photosensitive materials for development, and image-receiving materials thereof. The present invention is particularly preferably applied to a color light-sensitive material for thermal development and its image-receiving material. These light-sensitive materials, image-receiving materials, and heat-developed color image forming methods themselves are known, and for example, those described in JP-A-11-305400 can be applied.

[0037]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

An image receiving material M101 having the structure shown in Tables 1 and 2 was produced.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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Next, a method for producing a heat-developable color photosensitive material will be described. First, a method for producing a photosensitive silver halide emulsion will be described. Photosensitive silver halide emulsion (1) [Emulsion for fifth layer (680 nm photosensitive layer)] A solution (II) of the composition shown in Table 4 was added to an aqueous solution of the composition shown in Table 3 with sufficient stirring for 9 minutes and 10 seconds. The solution (I) was added over 9 minutes 10 seconds after the start of the addition of the solution (II). Five minutes after the completion of the addition of the solution (I), the solution (III) having the composition shown in Table 4 was added over 33 minutes, and simultaneously with the start of the addition of the solution (III), the solution (IV) was added over 34 minutes. Was added.

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

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Also, from 15 minutes after the start of the addition of the solution (III), 19
Aqueous solution 1 containing 0.473 g of sensitizing dye over a period of 1 minute
35 cc was added.

After washing with water and desalting (using a precipitant a at a pH of 3.6) according to a conventional method, 22 g of lime-treated ossein gelatin, 0.30 g of NaCl and an appropriate amount of NaOH were added to adjust the pH to 6 After adjusting the pAg to 7.9, p.
Chemically sensitized at ℃. For chemical sensitization, the compounds shown in Table 5 were added in order from the top. The yield of the resulting emulsion was 675 g, a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.25 µm. The pH of the finished emulsion was 6.15 (40 ° C.) and the viscosity was 5.4 centipoise (40 ° C.).

[0052]

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[0053]

[Table 5]

[0054]

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[0055]

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Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] A solution (II) of the composition shown in Table 7 was added to an aqueous solution of the composition shown in Table 6 with sufficient stirring. The solution (I) was simultaneously added over 17 minutes and 50 seconds from 10 seconds after the start of the addition of the solution (II). Five minutes after the completion of the addition of the solution (I), the solution (III) having the composition shown in Table 7 was added over 24 minutes, and simultaneously, the solution (IV) was added over 24 minutes and 30 seconds.

[0057]

[Table 6]

[0058]

[Table 7]

Lime-treated ossein gelatin (calcium content: 150 PPM) after washing with water, desalting (pH was set to 3.9 using sedimentation agent b) and decalcification in a conventional manner
22 g), redisperse at 40 ° C., add 0.39 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, adjust the pH to 5.9 and the pAg to 7.8. Was adjusted to Then, it was chemically sensitized at 60 ° C. For chemical sensitization, the compounds shown in Table 8 were added in order from the top. At the end of the chemical sensitization, the sensitizing dye was used as a methanol solution (Table 9).
(A solution having the composition shown in Table 1). In addition, 50 after chemical sensitization
The temperature was lowered to 0 ° C., and a gelatin dispersion 20 of a stabilizer described later was prepared.
After adding 0 g and stirring sufficiently, the mixture was stored. The yield of the resulting emulsion was 938 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 µm.

[0060]

[Table 8]

[0061]

[Table 9]

[0062]

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Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)]
(II) solution having the composition shown in
Ten seconds after the start of the addition of the solution (II), the solution (I) was added over 30 minutes. Five minutes after the completion of the addition of the liquid (I), the liquid (III) having the composition shown in Table 11 was added over 24 minutes, and simultaneously the liquid (IV) was added.
The solution was added over 23 minutes and 30 seconds.

[0064]

[Table 10]

[0065]

[Table 11]

After washing with water and desalting (using a precipitant a at a pH of 3.7) according to a conventional method, 22 g of lime-treated ossein gelatin was added, the pH was 7.4, and the pAg was 7.8. Was adjusted to Then, it was chemically sensitized at 60 ° C. Chemical sensitization
The compounds shown in Table 12 were added in order from the top. The yield of the obtained emulsion was 683 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.35 μm.

[0067]

[Table 12]

Next, a method for preparing a gelatin dispersion of colloidal silver will be described.

A solution having a composition shown in Table 14 was added to a sufficiently stirred aqueous solution having a composition shown in Table 13 over 24 minutes. Thereafter, the resultant was washed with a settling agent a, and then the pH was adjusted to 6.3 by adding 43 g of lime-treated ossein gelatin. The average particle size was 0.02 μm and the yield was 512 g. (Dispersion containing 2% silver and 6.8% gelatin)

[0070]

[Table 13]

[0071]

[Table 14]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Gelatin dispersions of a yellow dye-donating compound, a magenta dye-donating compound, and a cyan dye-donating compound were prepared according to the formulations shown in Table 15, respectively. That is, each oil phase component was heated and dissolved at about 70 ° C. to form a uniform solution. The aqueous phase component heated to about 60 ° C. was added to this solution, mixed with stirring, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion.
Further, a gelatin dispersion of a cyan dye-donating compound is subjected to an ultrafiltration module (Asahi Kasei ultrafiltration module; ACV-
3050), the dilution with water and concentration were repeated to reduce the amount of ethyl acetate to 1/7 of the amount of ethyl acetate in Table 15.

[0074]

[Table 15]

The gelatin dispersion of the antifoggant is shown in Table 1.
Preparation No. 6 was prepared as prescribed. That is, the oil phase component is heated and dissolved at about 60 ° C., and the heated aqueous phase component is added to this solution at about 60 ° C.
After stirring and mixing, 1000 minutes with a homogenizer.
The mixture was dispersed at 0 rpm to obtain a uniform dispersion.

[0076]

[Table 16]

A magenta dye-donating compound, a reducing agent,
Gelatin dispersions of the boiling point solvents were prepared according to the formulation in Table 17 (Dispersions A, B). That is, the oil phase component is heated and dissolved at about 60 ° C., the aqueous phase component heated to about 60 ° C. is added to the solution, and the mixture is stirred and mixed, and then mixed with a homogenizer for 10 minutes.
The mixture was dispersed at 000 rpm to obtain a uniform dispersion.

[0078]

[Table 17]

A gelatin dispersion of the reducing agent was prepared according to the recipe in Table 18. That is, the oil phase component is heated and dissolved at 60 ° C., the aqueous phase component heated to about 60 ° C. is added to the solution, and the mixture is stirred and mixed, and then homogenized for 10 minutes at 1000 rpm.
To obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using an organic solvent removal device under reduced pressure.

[0080]

[Table 18]

The dispersion of the polymer latex (a) is shown in Table 1.
Prepared according to Formulation No. 9. That is, an anionic surfactant was added over 10 minutes while stirring a mixture of the polymer latex (a), surfactant and water in the amounts shown in Table 19 to obtain a uniform dispersion. Further, the obtained dispersion is subjected to an ultrafiltration module (Asahi Kasei ultrafiltration module: ACV-305).
Using 0), the dilution with water was repeated and the concentration was repeated so that the dispersion had a salt concentration of 1/9.

[0082]

[Table 19]

A gelatin dispersion of the stabilizer was prepared according to the recipe in Table 20. That is, the oil phase component was dissolved at room temperature, the aqueous phase component heated to about 40 ° C. was added to the solution, and the mixture was stirred and mixed, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. This was mixed with water and stirred to obtain a uniform dispersion.

[0084]

[Table 20]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 21. That is, after mixing and dissolving each component, the mixture was dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.2
The thing of 5 μm was used. )

[0086]

[Table 21]

Next, a method for preparing a gelatin dispersion of a matting agent to be added to the protective layer will be described. PM in methylene chloride
The solution in which MA was dissolved was added to gelatin together with a small amount of a surfactant, and the mixture was stirred and dispersed at high speed. Subsequently, methylene chloride was removed using a vacuum desolvation apparatus, and the average particle size was 4.
A uniform dispersion of 3 μm was obtained.

Using the above materials, heat-developable color light-sensitive materials 101 shown in Tables 22, 23 and 24 were prepared. Here, the application amount refers to the application amount in a state where the liquid of each layer is applied. It does not refer to the amount of each layer applied when the liquid is dried.

[0089]

[Table 22]

[0090]

[Table 23]

[0091]

[Table 24]

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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Next, Sample 1 of the photothermographic material of the present invention was prepared.
In No. 01, Samples 102 to 104 of the present invention and Comparative Samples 105 to 108 were prepared by changing the additive materials of the seventh layer (uppermost layer) and the sixth layer (adjacent layer) as shown in Table 25. These samples were combined with the image receiving material M101, respectively, exposed to wedges, and then heat-developed by a digital color printer FUJICS PICTROGRAPHY PG-4000 manufactured by Fuji Photo Film Co., Ltd., and the degree of fogging was observed. On the other hand, in order to evaluate the coating surface condition,
Coating was performed with only the coating amount of the seventh layer (uppermost layer) of each sample being reduced to 1/6 (without changing other constituent layers), and the surface state was visually evaluated. The evaluation of cissing was performed by counting the number of cissing on the coated surface using an optical microscope. When the number of cissing was less than 11 / mm ² , it was evaluated as “○”, and when it was 11 / mm ² or more, it was evaluated as “×”. In addition, the applicability was evaluated by observing with naked eyes the places where the ears were cut off (poor application at both ends with respect to the application direction) and the degree of disturbance of the applied portion. "O" indicates that there are few cuts in the ears and the degree of disturbance of the painted portion is small, and "X" indicates that the number is large. Table 25 shows the obtained results.

[0106]

[Table 25]

The following can be seen from the results in Table 25. That is, in the samples 101 to 104 of the present invention, even if the type of the fluorine-based nonionic surfactant in the uppermost layer was changed, or the type of the polyvalent metal salt in the uppermost layer or the adjacent layer was changed, Good (evaluation ○) in terms of chargeability and suppression of fog.
Incidentally, the number of occurrences of repelling in the samples 101 to 104 of the present invention was 0 / mm ² . On the other hand, in the comparative sample 105 (control), the repelling failure occurs because the anionic surfactant is used in the uppermost layer even in the fluorine system. In addition, in Comparative Sample 106, it can be seen that the coated surface state (repelling and coating properties) is poor because the amount of the polyvalent metal salt used for the uppermost layer is small. Comparative sample 1
In No. 07, since an anionic surfactant was not used in the uppermost layer, the coated surface (repelling and coating properties) was poor, and the reducing agent (antifoggant) could not be emulsified, resulting in fogging (evaluation). X). In addition, in the comparative sample 108, since the polyvalent metal salt is not used for the uppermost layer, the applicability is poor. After applying and drying each sample, a charging test was performed in accordance with a usual method. As a result, there was no discharge and the charging was good (（).

[0108]

By adopting the constitution of the present invention, an unexpected effect that the failure of the coated surface condition (repelling and coating property) can be eliminated and the occurrence of charging and fogging can be suppressed can be obtained.

Claims (5)

[Claims] 1. A fluorine-containing nonionic surfactant, a polyvalent metal salt of 1.5 × 10 ⁻⁵ mol / m ² or more, and a polyvalent metal salt on the uppermost layer on the information recording layer side of the support. And an anionic surfactant which forms a sparingly soluble salt in an aqueous solution. 2. The information recording material according to claim 1, wherein a polyvalent metal salt and an anionic surfactant for forming a sparingly soluble salt with the polyvalent metal are contained in a lower layer adjacent to the uppermost layer. 3. The information recording material according to claim 1, wherein said information recording layer is a photosensitive silver halide emulsion layer. 4. A fluorine-containing nonionic surfactant is coated on a surface layer of the support on the side of the photosensitive silver halide emulsion layer, and 1.5 × 1
0 ^-5 mol / m ² or higher-valent metal salt and, heat-developable color photographic material further comprising an anionic surfactant to make the sparingly soluble salt with the polyvalent metal and an aqueous solution. 5. The heat-developable color photographic light-sensitive material according to claim 4, wherein a lower layer adjacent to the uppermost layer contains a polyvalent metal salt and an anionic surfactant for forming a sparingly soluble salt with the polyvalent metal. material.