(19)
(11) EP 1 109 065 A2

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication:
20.06.2001 Bulletin 2001/25

(21) Application number: 00126590.9

(22) Date of filing: 13.12.2000
(51) International Patent Classification (IPC)7: G03C 8/40
(84) Designated Contracting States:
AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR
Designated Extension States:
AL LT LV MK RO SI

(30) Priority: 13.12.1999 JP 35325299

(71) Applicant: FUJI PHOTO FILM CO., LTD.
Kanagawa-ken (JP)

(72) Inventors:
  • Nagahara, Tomoaki
    Minami-ashigara-shi, Kanagawa-ken (JP)
  • Hayashi, Gen
    Minami-ashigara-shi, Kanagawa-ken (JP)

(74) Representative: HOFFMANN - EITLE 
Patent- und Rechtsanwälte Arabellastrasse 4
81925 München
81925 München (DE)

   


(54) Information recording material


(57) An information recording material which contains a fluorine-containing nonionic surfactant, 1.5×10-5 mol/m2 or more of a polyvalent metal salt, and an anionic surfactant capable of forming a sparingly soluble salt in an aqueous solution with the polyvalent metal, in the outermost layer on a support on the side of an information recording layer. The information recording material is less in static charge and improved in surface deficiencies due to coating.


Description

FIELD OF THE INVENTION



[0001] The present invention relates to an information recording material, particularly to a silver halide color photographic light-sensitive material, especially to a heat-developable color photographic light-sensitive material, that is less in static charge and improved in coating deficiency.

BACKGROUND OF THE INVENTION



[0002] It is generally known that a fluorine-containing nonionic surfactant is used to decrease static charge of an information recording material, represented by a silver halide photographic light-sensitive material (e.g. JP-A-62-195649 ("JP-A" means unexamined published Japanese patent application)). In this case, the fluorine-containing nonionic surfactant is often added to an outermost layer. On the other hand, it is also known that, in the production of the information recording material, surface deficiencies, such as cissings, tend to occur when a plurality of hydrophilic layers are coated simultaneously onto a support conveyed at a velocity of 20 m/min or more, and various coating aids are used in the outermost layer to prevent such surface deficiencies. Also, in addition to the above compounds, matt agents, mordants, emulsions, and the like are sometimes added to the outermost layer, to provide various functions according to the purpose of the recording material to be used. If various additives are added at the same time to the outermost layer in this manner, to provide these various functions, these additives react with each other in the layer. This gives rise to the problem that surface deficiencies, which adversely affect product quality, are caused in a step of applying an information recording layer on a support, resulting in a significantly reduced product yield.

SUMMARY OF THE INVENTION



[0003] An object of the present invention is to provide an information recording material less in static charge and improved in surface deficiencies due to coating. Another object of the present invention is to provide a silver halide photographic light-sensitive material, in particular a heat-developable color photographic light-sensitive material, that is less in surface deficiencies even in a production method in which two or more layers are applied simultaneously on a support conveyed at a velocity of 20 m/min or more.

[0004] Other and further objects, features, and advantages of the invention will appear more fully from the following description.

DETAILED DESCRIPTION OF THE INVENTION



[0005] The inventors of the present invention, having conducted earnest studies, have found that the above objects can be attained by the following means.

(1) An information recording material comprising a fluorine-containing nonionic surfactant, 1.5×10-5 mol/m2 or more of a polyvalent metal salt, and an anionic surfactant capable of forming a sparingly soluble salt in an aqueous solution with the polyvalent metal, in the outermost layer on a support on the side of an information recording layer.

(2) The information recording material according to the above (1), wherein a polyvalent metal salt and an anionic surfactant capable of forming a sparingly soluble salt with the polyvalent metal are contained in an underlayer adjacent to the outermost layer.

(3) The information recording material according to the above (1) or (2), wherein the information recording layer is a light-sensitive silver halide emulsion layer.

(4) A heat-developable color photographic light-sensitive material comprising a fluorine-containing nonionic surfactant, 1.5×10-5 mol/m2 or more of a polyvalent metal salt, and an anionic surfactant capable of forming a sparingly soluble salt in an aqueous solution with the polyvalent metal, in a surface layer on a support on the side of a light-sensitive silver halide emulsion layer.

(5) The heat-developable color photographic light-sensitive material according to the above (4), wherein a polyvalent metal salt and an anionic surfactant capable of forming a sparingly soluble salt with the polyvalent metal are contained in an underlayer adjacent to the outermost layer.



[0006] Herein, the term "a sparingly soluble salt" means a salt having a solubility to water of generally 300 mg/100 g-water (20 °C) or less, preferably 20 mg/100 g-water (20 °C) or less.

[0007] The information recording material of the present invention will be hereinafter explained in detail.

[0008] It is effective that when two or more layers are coated simultaneously onto a support conveyed at a velocity of 20 m/min or more, a layer adjacent to the outermost layer of the information recording material is made to contain a polyvalent metal salt and an anionic surfactant capable of forming a sparingly soluble salt with the polyvalent metal, in order to improve coating property and to add other functions. However, contrary to the above, this method poses the problem that cissing deficiency tends to occur. The present invention is particularly effective to solve such a technical problem in the step of coating for the information recording material. Moreover, the present invention can particularly effectively solve the problem of coating deficiency of the information recording material having such an adjacent layer as described in the above (2) and (5).

[0009] The fluorine-containing nonionic surfactant which can be used in the information recording material of the present invention is described in, for example, U.K. Patent No. 1,330,356, JP-A-49-10722, JP-A-53-84712, JP-A-54-14224, JP-A-50-113221 and JP-A-62-195649. These fluorine-containing nonionic surfactants may be used in combinations of two or more.

[0010] Specific examples of preferable fluorine-containing nonionic surfactants are shown below, but the present invention is not limited to these.





































[0011] The amount of the fluorine-containing nonionic surfactant to be used in the present invention is preferably 0.0001 to 2.0 g, and particularly preferably 0.0005 to 0.1 g, per square meter of the information recording material.

[0012] Given as examples of the polyvalent metal salt for use in the outermost layer and a layer adjacent thereto may include calcium nitrate, magnesium nitrate, barium sulfate and zinc stearate. Among these salts, calcium nitrate is preferable, since it is soluble in water so that it is used with ease, as well as it is inert to other materials in the light-sensitive material.

[0013] It is necessary that the amount of the polyvalent metal salt to be used in the outermost layer be 1.5×10-5 mol/m2 or more, and the amount is preferably 2×10-5 mol/m2 to 1×10-4 mol/m2. The amount of the polyvalent metal salt to be used in the layer adjacent to the outermost layer is preferably 1×10-5 mol/m2 to 5 mol/m2. When the polyvalent metal salt is calcium nitrate, the amount thereof to be used is preferably 1×10-5 mol/m2 to 1×10-4 mol/m2.

[0014] These polyvalent metal salts may be used either singly or in combination of two or more, in each of the outermost layer or the layer adjacent thereto.

[0015] As the anionic surfactant which is used in the outermost layer and the layer adjacent thereto and which is capable of forming a sparingly soluble salt with the polyvalent metal in an aqueous solution, anionic surfactants described in, for instance, JP-A-6-138623 may be used.

[0016] The anionic group of the anionic surfactant for use in the present invention is a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, or the like, and the hydrophobic moiety of the anionic surfactant is a hydrocarbon, a partly or completely fluorinated hydrocarbon, or the like.

[0017] The anionic surfactant preferably used in the present invention is those represented by one of the following formulas (1) to (9). However, the anionic surfactant for use in the present invention is not limited to these compounds.









        R1-O-SO3M     (5)











[0018] In formula (1), R1 represents a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms or a fluorine-substituted group thereof, and examples of these groups include a propyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, octadecyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, heptacosafluorotridecyl group and tritriacontafluoroheptadecyl group; R2 represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms (e.g., a methyl group, ethyl group, n-propyl group and iso-propyl group); n is an integer from 1 to 20, among which 1 to 8 are particularly preferable; and M represents a monovalent alkali metal, and M is particularly preferably Na or K.

[0019] In formulas (2) and (3), R1, M and n have the same meanings as defined in formula (1); a is 0, 1 or 2, and m is an integer from 1 to 6 among which 2 to 4 are particularly preferable.

[0020] In formulas (4), (5) and (6), R1 and M have the same meanings as defined in formula (1).

[0021] In formula (7), R2 and M have the same meanings as defined in formula (1) and m has the same meaning as defined in formula (2).

[0022] In formulas (8) and (9), R3 represents a saturated or unsaturated hydrocarbon group which has 3 to 22 carbon atoms in which the hydrogen portion is fluorinated, and which is preferably such a hydrocarbon group having 7 to 18 carbon atoms (e.g., a pentadecafluoroheptyl group, heptadecafluorooctyl group, heptacosafluorotridecyl group or tritriacontafluoroheptadecyl group); R2 and M have the same meanings as defined in formula (1) and m has the same meaning as defined in formula (2).

[0023] Specific examples of the anionic surfactant which are particularly preferably used are as follows, but these are not intended to be limiting of the present invention.

        I - 1   C11H23CONHCH2SO3Na



        I - 2   C7F15CONH(CH2)2SO3Na

















        V-1   C7H15-O-SO3K   V-2   C12H25O-SO3Na







        VIII-1   C8F17-SO2NH(CH2)3COONa



        VIII-2   C17F33SO2NH(CH2)4COONa



        IX-1   C13F27SO2NH(CH2)3OPO(OH)2



[0024] These anionic surfactants may be used either singly or in combination of two or more, in each of the outermost layer or the layer adjacent thereto.

[0025] In the present invention, use can be made of the polyvalent metal salts and the anionic surfactants, each of which may be the same ones or different from each other as in the outermost layer and the layer adjacent thereto. In the present invention, it is preferable to use the same polyvalent metal salt and the same anionic surfactant, in the outermost layer and the layer adjacent thereto.

[0026] The information recording material of the present invention may be any type of information recording material which is produced by applying a hydrophilic colloidal layer on a support and which can record information. Specific examples of the information recording material include heat-sensitive recording materials, pressure-sensitive recording materials, light-sensitive materials and image-receiving materials for use in a diffusion-transfer system. Typical light-sensitive materials are silver halide photographic light-sensitive materials, including, for example, usual black-and-white silver halide light-sensitive materials (e.g., black-and-white light-sensitive materials for photographing, X-ray black-and-white light-sensitive materials, and black-and-white light-sensitive materials for printing), usual multilayer color light-sensitive materials (e.g., color papers, color reversal films, color negative films, color positive films, and color positive papers), color diffusion-transfer film units, black-and-white or color light-sensitive materials for heat development, and image-receiving materials therefor. The present invention is particularly preferably applied to color light-sensitive materials for heat development and image-receiving materials therefor. These light-sensitive materials and image-receiving materials, and the method of forming a color image via heat development themselves are known. For example, those described in JP-A-11-305400 may be applied to the present invention.

[0027] According to the present invention, it is possible to obtain such unexpected effects that defects (cissings and coating property deficiency) of the state of coated surface can be solved, as well as that electrification and the occurrence of fog can be suppressed.

[0028] The present invention is described in more detail with reference to the following examples, but the present invention is not limited thereto.

EXAMPLE


Example 1



[0029] Image-Receiving Material M101 having the constitution as shown in Tables 1 and 2 was made.
Table 1
Constitution of Image-Receiving Material M101
Number of layer Additive Coated amount (mg/m2)
Sixth layer Water-soluble polymer(1) 130
  Water-soluble polymer(2) 35
  Water-soluble polymer(3) 45
  Potassium nitrate 20
  Anionic surfactant(1) 6
  Anionic surfactant(2) 6
  Amphoteric surfactant(1) 50
  Stain-preventing agent(1) 7
  Stain-preventing agent(2) 12
  Matt agent(1) 7
Fifth layer Acid-processed gelatin 170
  Water-soluble polymer(5) 35
  Anionic surfactant(3) 6
  Matt agent(2) 140
  Hardener(1) 60
Forth layer Mordant(1) 1850
  Water-soluble polymer(2) 260
  Water-soluble polymer(4) 1400
  Dispersion of latex(1) 600
  Anionic surfactant(3) 25
  Nonionic surfactant(1) 18
  Guanidine picolinate 2550
  Sodium quinolinate 350
Third layer Gelatin 370
  Mordant(1) 300
  Anionic surfactant(3) 12
Second layer Gelatin 700
  Mordant(1) 290
  Water-soluble polymer(1) 55
  Anionic surfactant(3) 13
  Anionic surfactant(4) 2
  High-boiling organic solvent (1) 175
  Brightening agent(1) 2
  Stain-preventing agent(3) 8
  Guanidine picolinate 360
  Potassium quinolinate 45
First layer Acid-processed gelatin 290
  Anionic surfactant(1) 16
  Sodium metaborate 45
  Matt agent(3) 274
  Hardener(1) 310
Base(1) Polyethylene-Laminated Paper Support (thickness 215µm)


[0030] The coated amount of the dispersion of latex is in terms of the coated amount of the solid content of latex.





















Water-soluble polymer(1)
   Sumikagel L5-H(trade name: manufactured by Sumitomo Kagaku Co.)

Water-soluble polymer(2)
   Dextran(molecular weight 70,000)

Water-soluble polymer(3)
   κ (kappa)-Carrageenan (trade name: manufactured by Taito Co.)

Water-soluble polymer(4)
   MP polymer MP-102 (trade name: manufactured by Kuraray Co.)

Water-soluble polymer(5)
   Acryl-modified copolymer of polyvinyl alcohol (modification degree: 17%)

Dispersion of latex(1)
   L X - 4 3 8 (trade name: manufactured by Nippon Zeon Co.)

Matt agent(1)
   SYLOID 79 (trade name: manufactured by Fuji Davisson Kagaku Co.)

Matt agent(2)
   PMMA grains (average grain diameter 3 µm)

Matt agent(3)
   PMMA grains
(average grain diameter 4 µm)



[0031] Hereinafter, the method of producing a heat-developable color light-sensitive material will be explained.

[0032] A method of making each light-sensitive silver halide emulsion will be explained. Light-sensitive silver halide emulsion (1) (an emulsion for a fifth layer (680-nm light-sensitive layer)

[0033] A solution (II) having the composition shown in Table 4 was added to an aqueous solution, which was sufficiently stirred and had the composition shown in Table 3, over 9 minutes and 10 seconds; and a solution (I) was added over 9 minutes, after 10 seconds from the start of the addition of the solution (II). Further, a solution (III) having the composition shown in Table 4 was added over 33 minutes, after 5 minutes from the completion of the addition of the solution (I); and a solution (IV) was added over 34 minutes, in which the addition of the solutions (III) and (IV) was started at the same time.
Table 3
Composition
H2O 620 ml
Lime-processed gelatin 20 g
KBr 0.3 g
NaCI 2 g
Silver halide solvent ① 0.030 g
Sulfuric acid (1N) 15.5 ml
Temperature   50 °C
Table 4
  Solution (I) Solution (II) Solution (III) Solution (IV)
AgNO3 30.0 g - 70.0 g -
KBr - 13.65 g - 44.1 g
NaCI - 3.60 g - 2.42 g
K2lrCl6 - - - 0.031 mg
Total volume water to make 126 ml water to make 132 ml water to make 254 ml water to make 252 ml




[0034] After 15 min of the start of the addition of Solution (III), 135 ml of an aqueous solution containing 0.473g of Sensitizing Dye ① was added over 19 min.

[0035] After washing with water and desalting (that was carried out using Settling (Precipitating) Agent a, at a pH of 3.6) in a usual manner, 22 g of lime-processed ossein gelatin, 0.30g of NaCl, and a proper quantity of NaOH were added, and after adjusting the pH and pAg to 6.0 and 7.9 respectively, the chemical sensitization was carried out at 60 °C. For chemical sensitization, the compounds shown in Table 5 were added in order of description starting from the above. The yield of the resulting emulsion was 675 g. The emulsion was a monodispersion cubic silver chlorobromide emulsion of which the coefficient of variation was 10.2% and the average particle size was 0.25 µm. Also, this finished emulsion had a pH of 6.15 (40°C) and a viscosity of 5.4 cP (40°C).

Table 5
Chemicals used in chemical sensitization Added amount
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.15 g
Sodium thiosulfate 6 mg
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.15 g
Antifoggant ② 0.03 g
Antifoggant ① 0.09 g
Antiseptic ① 0.07 g
Antiseptic ② 3.13 g








Light-sensitive silver halide emulsion (2) (an emulsion for a Third layer (750-nm light-sensitive layer)

[0036] A solution (II) having the composition shown in Table 7 was added to an aqueous solution, which was sufficiently stirred and had the composition shown in Table 6, over 18 minutes; and a solution (I) was added over 17 minutes and 50 seconds, after 10 seconds from the start of the addition of the solution (II). A solution (III) having the composition shown in Table 7 was added over 24 minutes, after 5 minutes from the completion of the addition of the solution (I), and a solution (IV) was added over 24 minutes and 30 seconds, in which the addition of the solutions (III) and (IV) was started at the same time.
Table 6
Composition
H2O 620 ml
Lime-processed gelatin 20 g
KBr 0.3 g
NaCI 1.98 g
Silver halide solvent ① 0.030 g
Sulfuric acid (1N) 16 ml
Temperature   45 °C
Table 7
  Solution (I) Solution (II) Solution (III) Solution (IV)
AgNO3 30.0 g - 70.0 g -
KBr - 13.65 g - 44.1 g
NaCI - 3.59 g - 2.39 g
K4[Fe(CN)6]·H2O - - - 65 mg
k2lrCl6 - - - 0.040 mg
Total volume water to make 180 ml water to make 180 ml water to make 247 ml water to make 250 ml


[0037] After washing with water and desalting (that was carried out using the above Settling Agent b at a pH of 3.9) in a usual manner, 22 g of lime-processed ossein gelatin from which calcium had been removed (the calcium content: 150 ppm or less) was added, re-dispersing was made at 40 °C, 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added, and the pH and pAg were adjusted to 5.9 and 7.8, respectively. Thereafter the chemical sensitization was carried out at 60 °C. For chemical sensitization, the compounds shown in Table 8 were added in order of description from the above. At the end of the chemical sensitization, Sensitizing Dye ② in the form of a methanol solution (the solution having the composition shown in Table 9) was added. After the chemical sensitization, the temperature was lowered to 50 °C and then 200 g of a gelatin dispersion of the later-described Stabilizer ① was added, followed by stirring well and keeping in a case. The yield of the thus-obtained emulsion was 938 g, and the emulsion was a monodispersed cubic silver chlorobromide emulsion having a deviation coefficient of 12.6% and an average grain size of 0.25 µm.
Table 8
Chemicals used in chemical sensitization Added amount
Triethylthiourea 3.1 mg
Nucleic acid decomposition product 0.39 g
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.29 g
NaCI 0.15 g
KI 0.12 g
Antifoggant ② 0.08 g
Antiseptic ① 0.07 g
Table 9
Composition of dye solution Added Added amount
Sensitizing dye ② 0.18 g
Methanol 18.7 ml




Light-sensitive silver halide emulsion (3) (an emulsion for a first layer (810-nm light-sensitive layer)

[0038] A solution (II) having the composition shown in Table 11 was added to an aqueous solution, which was sufficiently stirred and had the composition shown in Table 10, over 30 minutes and 10 seconds; and a solution (I) was added over 30 minutes, after 10 seconds from the start of the addition of the solution (II). A solution (III) having the composition shown in Table 11 was added over 24 minutes, after 5 minutes from the completion of the addition of the solution (I), and a solution (IV) was added over 23 minutes and 30 seconds, in which the addition of the solutions (III) and (IV) was started at the same time.
Table 10
Composition
H2O 620 ml
Lime-processed gelatin 20 g
KBr 0.3 g
NaCI 2 g
Silver halide solvent ① 0.030 g
Sulfuric acid (1N) 15.5 ml
Temperature   50 °C
Table 11
  Solution (I) Solution (II) Solution (III) Solution (IV)
AgNO3 30.0 g - 70.0 g -
KBr - 13.65 g - 44.1 g
NaCI - 3.6 g - 2.4 g
K2lrCl6 - - - 0.020 mg
Yellow prussiate of patash - - - 0.04 g
Total volume water to make 180 ml water to make 180 ml water to make 248 ml water to make 241 ml


[0039] After washing with water and desalting (that was carried out using the Settling Agent a, at a pH of 3.7) in a usual manner, 22 g of lime-processed ossein gelatin was added, and after adjusting the pH and pAg to 7.4 and 7.8 respectively, the chemical sensitization was carried out at 60 °C. For chemical sensitization, the compounds shown in Table 12 were added in order of description from the above. The yield of the resulting emulsion was 683 g. The emulsion was a monodispersion cubic silver chlorobromide emulsion of which the coefficient of variation was 9.7% and the average particle size was 0.35 µm.
Table 12
Chemicals used in chemical sensitization Added amount
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.125 g
Triethylthiourea 1.98 mg
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.125 g
Antifoggant ② 0.16 g
Antiseptic ① 0.07 g
Antiseptic ② 3 g


[0040] The preparation method of a gelatin dispersion of colloidal silver is described.

[0041] To a well-stirred aqueous solution having the composition shown in Table 13, was added a Solution having the composition shown in Table 14, over 24 min. Thereafter, the washing with water using Settling Agent a was carried out, then 43 g of lime-processed ossein gelatin was added, and the pH was adjusted to 6.3. The average grain size of the thus-obtained grains in the dispersion was 0.02 µm and the yield was 512 g. (The dispersion was a dispersion containing silver 2% and gelatin 6.8%.)
Table 13
Composition
H2O 620 ml
Dextrin 16 g
NaOH(5N) 41 ml
Temperature 30 °C
Table 14
Composition
H2O 135 ml
AgNO3 17 g


[0042] The preparation methods of gelatin dispersions of hydrophobic additives are described.

[0043] Gelatin dispersions of a yellow dye-providing compound, a magenta dye-providing compound, or a cyan dye-providing compound whose formulation are shown in Table 15, were prepared, respectively. That is, the oil phase components were dissolved by heating to about 70 °C, to form a uniform solution, and to the resultant solution, was added the aqueous phase components that had been heated to about 60 °C, followed by stirring to mix and dispersing by a homogenizer for 10 min at 10,000 rpm. To the resultant dispersion, was added additional water, followed by stirring, to obtain a uniform dispersion. Further, by using an ultrafiltration module (Ultrafiltration Module ACV-3050, trade name, manufactured by Asahi Chemical Industry Co., Ltd.), the gelatin dispersion of the cyan dye-providing compound was repeatedly diluted with water and concentrated to decrease the amount of ethyl acetate so that the amount might become 1/17.6 of the amount of ethyl acetate shown in Table 15.



[0044] A gelatin dispersion of Antifoggant ④ whose formulation is shown in Table 16 was prepared. That is, the oil phase components were dissolved by heating to about 60 °C, to the resultant solution, was added the aqueous phase components that had been heated to about 60 °C, and after stirring and mixing them, the resultant mixture was dispersed for 10 min at 10,000 rpm by a homogenizer, to obtain a uniform dispersion.
Table 16
    Composition of dispersion of
Oil phase Oil phase Antifoggant ④ 0,8 g
Reducing agent ① 0.1 g
High-boiling solvent ② 2.3 g
High-boiling solvent ⑤ 0.2 g
Surfactant ① 0.5 g
Surfactant ④ 0.5 g
Ethyl acetate 10.0 ml
Aqueous phase Lime-processed gelatin 10.0 g
Calcium nitrate 0.1 g
Antiseptic ① 0.004 g
Water Water 45.2 ml 45.2 ml
  Additional water after emulsification and dispersing 35.0 ml


[0045] A gelatin dispersion of Magenta dye-providing compound ② , Reducing agent ② , and High-boiling solvent ① whose formulation is shown in Table 17 was prepared (Dispersions A, B). That is, the oil phase components were dissolved by heating to about 60 °C, to the resultant solution, was added the aqueous phase components that had been heated to about 60 °C, and after stirring and mixing them, the resultant mixture was dispersed for 10 min at 10,000 rpm by a homogenizer, to obtain a uniform dispersion.
Table 17
    Composition of dispersion
Oil phase Magenta dye-providing compound ② 0.13 g
Reducing agent ② 0.07 g
High-boiling solvent ① 9.1 g
High-boiling solvent ⑤ 0.2 g
Surfactant ① 0.5 g
Surfactant ④ 0.5 g
Ethyl acetate 10.0 ml
Aqueous phase Lime-processed gelatin 10.0 g
Calcium nitrate 0.1 g
Antiseptic ① 0.004 g
Water 74.1 ml
  Additional water after emulsification and dispersing 104.0 ml


[0046] A gelatin dispersion of Reducing Agent ② whose formulation is shown in Table 18 was prepared. That is, the oil phase components were dissolved by heating to about 60 °C, to the resultant solution, was added the aqueous phase components that had been heated to about 60 °C, and after stirring and mixing them, the resultant mixture was dispersed for 10 min at 1,000 rpm by a homogenizer, to obtain a uniform dispersion. From the thus-obtained dispersion, ethyl acetate was removed off using a vacuum organic solvent removing apparatus.
Table 18
    Composition of dispersion
Oil phase Reducing agent ② 7.5 g
High-boiling solvent ① 4.7 g
Surfactant ① 1.9 g
Ethyl acetate 14.4 ml
Aqueous phase Acid-processed gelatin 10.0 g ml
Antiseptic ① 0.02 g
Antiseptic ③ 0.04 g
Sodium bisulfite 0.1 g
Water 136.7 ml


[0047] A dispersion of Polymer Latex(a) whose formulation is shown in Table 19 was prepared. That is, to a mixed solution of Polymer Latex (a), Surfactant ⑤ , and water, whose amounts are shown in Table 19, with stirring, Anionic Surfactant ⑦ was added, over 10 min, to obtain a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated, using a ultrafiltration module (Ultrafiltration Module: ACV-3050, trade name, manufactured by Ashahi Chemical Industry Co., Ltd.), to bring the salt concentration of the dispersion to 1/9, thereby obtaining the intended dispersion.
Table 19
  Composition of dispersion
Polymer Latex a aqueous solution (solid content 13%) 108.1 ml
Surfactant ⑤ 20.0 g
Surfactant ⑦ aqueous solution(5%) 600.0 ml
Water 1232.0 ml


[0048] A gelatin dispersion of Stabilizer ① whose formulation is shown in Table 20 was prepared. That is, the oil phase components were dissolved at room temperature, to the resultant solution, were added the aqueous phase components that had been heated to about 40 °C, and after stirring and mixing them, the resultant mixture was dispersed for 10 min at 10,000 rpm by a homogenizer. To the resultant dispersion, was added additional water, followed by stirring, thereby obtaining a uniform dispersion.
Table 20
    Composition of dispersion
Oil phase Stabilizer ① 4.0 g
Sodium hydroxide 0.3 g
Methanol 62.8 g
High-boiling solvent ④ 0.9 g
Aqueous phase Gelatin from which calcium had been removed (Ca content 100 ppm or less) 10.0 g
Antiseptic ① 0.04 g
Water 320.5 ml


[0049] A gelatin dispersion of zinc hydroxide was prepared according to the formulation shown in Table 21. That is, after the components were mixed and dissolved together, dispersing was carried out for 30 min in a mill, using glass beads having an average particle diameter of 0.75 mm. Then the glass beads were separated and removed off, to obtain a uniform dispersion. (The zinc hydroxide having an average particle size of 0.25 µm was used.)
Table 21
  Composition of dispersion
Zinc hydroxide 15.9 g
Carboxymethyl cellulose 0.7 g
Poly(sodium acrylate) 0.07 g
Lime-processed gelatin 4.2 g
Water 100 ml
High-boiling solvent ④ 0.4 g


[0050] The preparation method of a gelatin dispersion of a matt agent that was to be added to the protective layer is described.

[0051] A solution containing PMMA dissolved in methylene chloride was added, together with a small amount of a surfactant, to gelatin, and they were stirred and dispersed at high speed. Then the methylene chloride was removed off using a vacuum solvent removing apparatus, to obtain a uniform dispersion having an average particle size of 4.3 µm.

[0052] Using the above materials, Heat-Developable Color Light-Sensitive Material 101, as shown in Tables 22 and 23, was prepared. The amount to be coated referred to herein indicates the amount to be coated in the state that the solution of each layer is applied, and it does not indicate the amount to be coated of each applied layer in the state that the solution is dried. The Antispetic ④ shown below was added to in the seventh layer in an appropriate amount.
Table 22
Constitution of Main Materials of Heat-Developable Light-Sensitive Material 101
Number of layer Name of layer Additive Coated amount (mg/m2)
Seventh layer Protective layer Acid-processed gelatin 629
Reducing agent ② 47
High-boiling solvent ① 30
Colloidal silver grains 2
Matt agent(PMMA resin) 17
Surfactant ② 0.4
Surfactant ① 12
Surfactant ③ 1.6
Polymer Latex (a) 30
Surfactant ⑥ 19
Surfactant ⑦ 25
Calcium nitrate 6.1
Sixth layer Intermediate Lime-processed gelatin 668
layer Antifoggant ④ 12
Reducing agent ① 1.5
High-boiling solvent ② 35
High-boiling solvent ⑤ 3.5
Surfactant ① 72
Surfactant ② 1.2
Surfactant ④ 7.2
Surfactant ⑤ 48
Zinc hydroxide 373
Water-soluble polymer ① 7.2
Calcium nitrate 13
Fifth layer Red-light-sensitive layer Lime-processed gelatin 451
Light-sensitive silver halide emulsion in terms of
(1) silver 299
Magenta dye-providing compound ① 410
High-boiling solvent ② 308
Reducing agent ① 6
Development accelerator ① 64
Antifoggant ④ 20
Surfactant ① 22
Water-soluble polymer ① 8.2
Calcium nitrate 4.2
Forth layer Intermediate layer Lime-processed gelatin 669
Antifoggant ④ 12
Reducing agent ① 1.5
High-boiling solvent ② 35
High-boiling solvent ⑤ 3.5
Surfactant ① 7.2
Surfactant ② 1.2
Surfactant ④ 7.2
Surfactant ⑤ 49
Zinc hydroxide 374
Water-soluble polymer ① 7.2
Calcium nitrate 13
Third layer The second infrared light-sensitive layer Lime-processed gelatin 391
Light-sensitive silver in terms of
halide emulsion(2) silver 134
Stabilizer ① 11.5
Cyan dye-providing compound ① 351
Cyan dye-providing compound ② 40
Dye(a) 11
High-boiling solvent ① 105
High-boiling solvent ② 112
Reducing agent ① 46
Antifoggant ③ 4.8
Surfactant ① 12
Carboxymethyl cellulose 5.8
Water-soluble polymer ① 12
Second layer Intermediate layer Lime-processed gelatin 526
Magenta dye-providing compound ② 1.8
Reducing agent ② 0.93
High-boiling solvent ① 128
High-boiling solvent ⑤ 3.2
Surfactant ① 6.6
Surfactant ④ 6.6
Surfactant ⑤ 17
Antifoggant ⑤ 3.4
Water-soluble polymer ① 26
Calcium nitrate 12
First layer The second infrared light-sensitive layer Lime-processed gelatin 629
Light-sensitive silver in terms of
halide emulsion(3) silver 331
Stabilizer ① 18
Yellow dye-providing compound ① 396
Sensitizing dye ③ 0.12
Dye(a) 46
High-boiling solvent ① 198
Reducing agent ① 71
Development accelerator ① 25
Antifoggant ③ 6.8
Surfactant ④ 45
Water-soluble polymer ② 42
Hardener ① 59
Base (2) Paper support laminated with polyethylene
Table 23
Constitution of Support Base (2)
Name of layer Composition Film thickness (µm)
Surface undercoat layer Gelatin 0.1 0.1
Surface PE layer layer Low-density polyethylene (Density 0.923) :89.2 parts Surface-processed titanium oxide :10.0 parts Ultramarine :0.8 parts 36.0
Pulp layer Fine quality paper (LBKP/NBSP=1/1, Density 1.080) 64.0
Back-surface PE layer High-density polyethylene (Density 0.960) 31.0
Back-surface undercoat layer Gelatin 0.05
Colloidal silica 0.05
   The total of film thickness 131.2












































(EMPARA 40(trade name: manufactured by Ajinomoto K.K.))











[0053] Samples 102 to 104 according to the present invention and Samples 105 to 108 for comparison were prepared in the same manner as the above heat-developable light-sensitive material Sample 101 according to the present invention, except that the additive materials in each of the seventh layer (outermost layer) and the sixth layer (adjacent layer) were changed, as shown in Table 24. Each of these Samples and the above Image-Receiving Material M101 were combined together respectively, and they were subjected to wedge exposure to light. Each of these combinations was then processed via heat development using a digital color printer Fujix Pictrography PG-4000 (trade name, manufactured by Fuji Photo Film Co., Ltd.), to observe the degree of occurrence of fogging.

[0054] On the other hand, in order to evaluate the state of coated surface, another set of the corresponding Samples were prepared in the same manner as in the above, except that only the amount to be coated in the seventh layer (outermost layer) was decreased to 1/6 in amount (while other structural layers were not changed in coated amount) when coating. The surface state of the thus-prepared Samples was evaluated with naked eyes. The evaluation of cissings was made by counting the number of cissings on the coated surface with an optical microscope. The case when the number of cissings was less than 11/mm2 was rated as "○ (good)", and the case when the number of cissings was 11/mm2 or more was rated as "× (poor)". The evaluation of coating property was made by observing, with naked eyes, both the coat-cut portions at edges (coating deficiency at both the right and left ends in the coating direction) and the degree of disorder of the coated parts. The case when the number of the coat-cut portions at edges was small and the degree of disorder of the coated parts was low was rated as "○", and the case when the number of the coat-cut portions at edges was large and the degree of disorder of the coated parts was high was rated as "×".

[0055] The obtained results are shown in Table 24.





[0056] The following facts can be understood from the results as shown in Table 24.

[0057] Specifically, the Samples 101 to 104 according to the present invention each were good (evaluation:○) in view of state of coated surface, antistatic property, and suppression of fogging, even if the type of fluorine-containing nonionic surfactant in the outermost layer was altered, or even if the type of polyvalent metal salt in the outermost layer or the layer adjacent to the outermost layer was altered. Incidentally, the number of cissing in each of the Samples 101 to 104 according to the present invention was 0/mm2 (not occurred at all).

[0058] On the contrary, with respect to the Comparative sample 105 (control), it is found that cissing deficiency was caused, because not a nonionic surfactant but an anionic surfactant was used in the outermost layer although the anionic surfactant was a fluorine-containing type. Also, regarding the Comparative sample 106, it is found that the state of coated surface (cissings and coating property) was poor, because the amount of the polyvalent metal salt to be used in the outermost layer was too small. With respect to the Comparative sample 107, the state of coated surface (cissings and coating property) was poor, as well as the Reducing agent ② (antifoggant) could not be emulsified, thereby causing fog (evaluation: X), because no anionic surfactant was used in the outermost layer. Regarding the Comparative sample 108, it is found that the coating property was poor, because no polyvalent metal salt was used in the outermost layer.

[0059] In addition, after applied and dried, each sample was subjected to an antistatic property test according to a usual method. As a result, no discharge from each of the samples was observed, showing that each sample was good in antistatic property (evaluation:○).

[0060] Having described our invention as related to the present embodiments, it is our intention that the invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.


Claims

1. An information recording material comprising a fluorine-containing nonionic surfactant, 1.5×10-5 mol/m2 or more of a polyvalent metal salt, and an anionic surfactant capable of forming a sparingly soluble salt in an aqueous solution with the polyvalent metal, in the outermost layer on a support on the side of an information recording layer.
 
2. The information recording material according to claim 1, wherein the fluorine-containing nonionic surfactant is selected from the group consisting of:




































 
3. The information recording material according to claim 1, wherein the polyvalent metal salt is calcium nitrate, magnesium nitrate, barium sulfate or zinc stearate.
 
4. The information recording material according to claim 1, wherein the anionic surfactant is represented by one of the following formulas (1) to (9):









        R1-O-SO3M     (5)









wherein, in formula (1), R1 represents a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms or a fluorine-substituted group thereof; R2 represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; n is an integer from 1 to 20; and M represents a monovalent alkali metal;

in formulas (2) and (3), R1, M and n have the same meanings as defined in formula (1); a is 0, 1 or 2, and m is an integer from 1 to 6;

in formulas (4), (5) and (6), R1 and M have the same meanings as defined in formula (1);

in formula (7), R2 and M have the same meanings as defined in formula (1), and m has the same meaning as defined in formula (2);

in formulas (8) and (9), R3 represents a saturated or unsaturated hydrocarbon group which has 3 to 22 carbon atoms in which the hydrogen portion is fluorinated; R2 and M have the same meanings as defined in formula (1), and m has the same meaning as defined in formula (2).


 
5. The information recording material according to claim 1, wherein a polyvalent metal salt and an anionic surfactant capable of forming a sparingly soluble salt with the polyvalent metal are contained in an underlayer adjacent to the outermost layer.
 
6. The information recording material according to claim 5, wherein the polyvalent metal salt in the underlayer is calcium nitrate, magnesium nitrate, barium sulfate or zinc stearate.
 
7. The information recording material according to claim 5, wherein the anionic surfactant in the underlayer is represented by one of the following formulas (1) to (9):









        R1-O-SO3M     (5)









wherein, in formula (1), R1 represents a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms or a fluorine-substituted group thereof; R2 represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; n is an integer from 1 to 20; and M represents a monovalent alkali metal;

in formulas (2) and (3), R1, M and n have the same meanings as defined in formula (1); a is 0, 1 or 2, and m is an integer from 1 to 6;

in formulas (4), (5) and (6), R1 and M have the same meanings as defined in formula (1);

in formula (7), R2 and M have the same meanings as defined in formula (1), and m has the same meaning as defined in formula (2);

in formulas (8) and (9), R3 represents a saturated or unsaturated hydrocarbon group which has 3 to 22 carbon atoms in which the hydrogen portion is fluorinated; R2 and M have the same meanings as defined in formula (1), and m has the same meaning as defined in formula (2).


 
8. The information recording material according to claim 5, wherein the polyvalent metal salts are the same ones as in the outermost layer and the underlayer adjacent thereto, and the anionic surfactants are the same ones as in the outermost layer and the underlayer adjacent thereto.
 
9. The information recording material according to claim 1, wherein the information recording layer is a light-sensitive silver halide emulsion layer.
 
10. A heat-developable color photographic light-sensitive material comprising a fluorine-containing nonionic surfactant, 1.5×10-5 mol/m2 or more of a polyvalent metal salt, and an anionic surfactant capable of forming a sparingly soluble salt in an aqueous solution with the polyvalent metal, in a surface layer on a support on the side of a light-sensitive silver halide emulsion layer.
 
11. The heat-developable color photographic light-sensitive material according to claim 10, wherein the fluorine-containing nonionic surfactant is selected from the group consisting of:




































 
12. The heat-developable color photographic light-sensitive material according to claim 10, wherein the polyvalent metal salt is calcium nitrate, magnesium nitrate, barium sulfate or zinc stearate.
 
13. The heat-developable color photographic light-sensitive material according to claim 10, wherein the anionic surfactant is represented by one of the following formulas (1) to (9):









        R1-O-SO3M     (5)









wherein, in formula (1), R1 represents a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms or a fluorine-substituted group thereof; R2 represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; n is an integer from 1 to 20; and M represents a monovalent alkali metal;

in formulas (2) and (3), R1, M and n have the same meanings as defined in formula (1); a is 0, 1 or 2, and m is an integer from 1 to 6;

in formulas (4), (5) and (6), R1 and M have the same meanings as defined in formula (1);

in formula (7), R2 and M have the same meanings as defined in formula (1), and m has the same meaning as defined in formula (2);

in formulas (8) and (9), R3 represents a saturated or unsaturated hydrocarbon group which has 3 to 22 carbon atoms in which the hydrogen portion is fluorinated; R2 and M have the same meanings as defined in formula (1), and m has the same meaning as defined in formula (2).


 
14. The heat-developable color photographic light-sensitive material according to claim 10, wherein a polyvalent metal salt and an anionic surfactant capable of forming a sparingly soluble salt with the polyvalent metal are contained in an underlayer adjacent to the outermost layer.
 
15. The heat-developable color photographic light-sensitive material according to claim 10, wherein the polyvalent metal salt in the underlayer is calcium nitrate, magnesium nitrate, barium sulfate or zinc stearate.
 
16. The heat-developable color photographic light-sensitive material according to claim 10, wherein the anionic surfactant in the underlayer is represented by one of the following formulas (1) to (9):









        R1-O-SO3M     (5)









wherein, in formula (1), R1 represents a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms or a fluorine-substituted group thereof; R2 represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; n is an integer from 1 to 20; and M represents a monovalent alkali metal;

in formulas (2) and (3), R1, M and n have the same meanings as defined in formula (1); a is 0, 1 or 2, and m is an integer from 1 to 6;

in formulas (4), (5) and (6), R1 and M have the same meanings as defined in formula (1);

in formula (7), R2 and M have the same meanings as defined in formula (1), and m has the same meaning as defined in formula (2);

in formulas (8) and (9), R3 represents a saturated or unsaturated hydrocarbon group which has 3 to 22 carbon atoms in which the hydrogen portion is fluorinated; R2 and M have the same meanings as defined in formula (1), and m has the same meaning as defined in formula (2).


 
17. The heat-developable color photographic light-sensitive material according to claim 10, wherein the polyvalent metal salts are the same ones as in the outermost layer and the underlayer adjacent thereto, and the anionic surfactants are the same ones as in the outermost layer and the underlayer adjacent thereto.