EP1109065B1

EP1109065B1 - Information recording material

Info

Publication number: EP1109065B1
Application number: EP00126590A
Authority: EP
Inventors: Tomoaki Nagahara; Gen Hayashi
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1999-12-13
Filing date: 2000-12-13
Publication date: 2006-03-08
Anticipated expiration: 2020-12-13
Also published as: EP1109065A3; EP1109065A2; JP2001166421A; DE60026430D1; ATE320028T1; DE60026430T2

Abstract

An information recording material which contains a fluorine-containing nonionic surfactant, 1.5x10<-5> mol/m<2> 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

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

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.
JP-A-62 275 245 discloses a silver halide photographic light-sensitive material, having, on a support at least one layer comprising a silver halide emulsion and in at least one hydrophilic colloid layer

a) at least one non-ionic surfactant,
b) at least one salt represented by any of formulae (I)-(IV), and
c) at least anionic surfactant having a polyoxyethylene group.

The cation M of this salt represents an alkali metal, an alkali earth metal or NH₄. The non-ionic surfactant to be used in not specifically limited. Two of altogether 12 concrete examples thereof are fluorine-containing non-ionic surfactants. The working examples of this document do not make use of these fluorine-containing non-ionic surfactants. This document aims at improving anti-static properties and is primarily concerned with reducing trouble due to the contamination of a developing solution in an autoprocessor.

SUMMARY OF THE INVENTION

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

DETAILED DESCRIPTION OF THE INVENTION

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.

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.
The information recording material of the present invention will be hereinafter explained in detail.
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).
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.
Specific examples of preferable fluorine-containing nonionic surfactants are shown below, but the present invention is not limited to these.
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.
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.
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.
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.
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.
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.
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)
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.
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.
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, 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).
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-I 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
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.
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.
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.
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.
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

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)

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)
LX-4 3 8 (trade name: manufactured by Nippon Zeon Co.)
Matt agent(1) (trade name: manufactured by SYLOID 79 Fuji Davisson Kagaku Co.)
Matt agent (2) PMMA grains (average grain diameter 3 µm)
Matt agent (3) PMMA grains (average grain diameter 4 µm)

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

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 solvent①	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
NaCl	-	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

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.

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
Antifoggant②	0.03 g
Antifoggant①	0.09 g
Antiseptic①	0.07 g
Antiseptic②	3.13 g

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

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
NaCl	1.98 g
Silver halide solvent①	0.030 g
Sulfuric acid (1N)	1-6 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
NaCl	-	3.59 g	-	2.39 g
K₄[Fe(CN)₆]·H₂O	-	-	-	65 mg
K₂IrCl₆	-	-	-	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

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
NaCl	0.15 g
KI	0.12 g
Antifoggant②	0.08 g
Antiseptic①	0.07 g

Table 9

Composition of dye solution	Added amount
Sensitizing dye②	0.18 g
Methanol	18.7 ml

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

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
NaCl	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
NaCl	-	3.6 g	-	2.4 g
K₂IrCl₆	-	-	-	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

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
Antifoggant②	0.16 g
Antiseptic①	0.07 g
Antiseptic②	3 g

The preparation method of a gelatin dispersion of colloidal silver is described.
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
The preparation methods of gelatin dispersions of hydrophobic additives are described.
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.

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
Oil phase	Antifoggant④	0.8 g
	Reducing agent①	0.1 g
	High-boiling solvent②	2.3 g
	High-boiling solvent⑤	0.2 g
	Surfactant①	0.5 g
	Surfactant④	0.5 g
	Ethyl acetate	10.0 ml
Aqueous phase	Lime-processed gelatin	10.0 g
	Calcium nitrate	0.1 g
	Antiseptic①	0.004 g
	Water	45.2 ml
	Additional water after emulsification and dispersing	35.0 ml

A gelatin dispersion of Magenta dye-providing compound②, Reducing agent②, and High-boiling solvent① 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 agent②	0.07 g
	High-boiling solvent①	9.1 g
	High-boiling solvent⑤	0.2 g
	Surfactant①	0.5 g
	Surfactant④	0.5 g
	Ethyl acetate	10.0 ml
Aqueous phase	Lime-processed gelatin	10.0 g
	Calcium nitrate	0.1 g
	Antiseptic①	0.004 g
	Water	74.1 ml
	Additional water after emulsification and dispersing	104.0 ml

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 agent②	7.5 g
	High-boiling sotvent①	4.7 g
	Surfactant①	1.9 g
	Ethyl acetate	14.4 ml
Aqueous phase	Acid-processed gelatin	10.0 g
	Antiseptic①	0.02 g
	Antiseptic③	0.04 g
	Sodium bisulfite	0.1 g
	Water	136.7 ml

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

Surfactant⑤ 20.0 g

Surfactant ⑦ aqueous solution(5%) 600.0 ml

Water 1232.0 ml

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	Stabilizer①	4.0 g
	Sodium hydroxide	0.3 g
	Methanol	62.8 g
	High-boiling solvent④	0.9 g
Aqueous phase	Gelatin from which calcium had been removed (Ca content 100 ppm or less)	10.0 g
	Antiseptic①	0.04 g
	Water	320.5 ml

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 solvent④ 0.4 g
The preparation method of a gelatin dispersion of a matt agent that was to be added to the protective layer is described.
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.

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 agent②	47
		High-boiling solvent①	30
		Colloidal silver grains	2
		Matt agent(PMMA resin)	17
		Surfactant②	0.4
		Surfactant①	12
		Surfactant③	1.6
		Polymer Latex (a)	30
		Surfactant⑥	19
		Surfactant②	25
		calcium nitrate	6.1
Sixth layer	Intermediate layer	Lime-processed gelatin	668
		Antifoggant④	12
		Reducing agent①	1.5
		High-boiling solvent②	35
		High-boiling solvent⑤	3.5
		Surfactant①	72
		Surfactant②	1.2
		Surfactant④	7.2
		Surfactant⑤	48
		Zinc hydroxide	373
		Water-soluble polymer①	7.2
		Calcium nitrate	13
Fifth layer	Red-light-sensitive layer	Lime-processed gelatin	451
		Light-sensitive silver halide emulsion (1)	in terms of silver 299
		Magenta dye-providing compound①	410
		High-boiling solvent②	308
		Reducing agent①	6
		Development accelerator①	64
		Antifoggant④	20
		Surfactant①	22
		Water-soluble polymer①	8.2
		Calcium nitrate	4.2
Forth layer	Intermediate layer	Lime-processed gelatin	669
		Antifoggant④	12
		Reducing agent①	1.5
		High-boiling solvent②	35
		High-boiting solvent⑤	3.5
		Surfactant①	7.2
		Surfactant②	1.2
		Surfactant④	7.2
		Surfactant⑤	49
		Zinc hydroxide	374
		Water-soluble polymer①	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
		Stabilizer①	11.5
		Cyan dye-providing compound①	351
		Cyan dye-providing compound②	40
		Dye(a)	11
		High-boiling solvent①	105
		High-boiling solvent②	112
		Reducing agent①	46
		Antifoggant③	4.8
		Surfactant①	12
		Carboxymethyl cellulose	5.8
		Water-soluble polymer①	12
Second layer	Intermediate layer	Lime-processed gelatin	526
		Magenta dye-providing compound②	1.8
		Reducing agent②	0.93
		High-boiling solvent①	128
		High-boiling solvent⑤	3.2
		Surfactant①	6.6
		Surfactant④	6.6
		Surfactant⑤	17
		Antifoggant⑤	3.4
		Water-soluble polymer①	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
		Stabilizer①	18
		Yellow dye-providing compound①	396
		Sensitizing dye③	0.12
		Dye(a)	46
		High-boiling solvent①	198
		Reducing agent①	71
		Development accelerator①	25
		Antifoggant③	6.8
		Surfactant①	45
		Water-soluble polymer②	42
		Hardener①	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
Surface PE layer PE	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

Hardener ① CH₂=CHSO₂CH₂SO₂CH=CH₂

High-boiling organic solvent ⑤ C₂₄H₄₄Cl₆ (EMPARA 40 (trade name: manufactured by Ajinomoto K.K.))

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.
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 "×".
The obtained results are shown in Table 24.
The following facts can be understood from the results as shown in Table 24.
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).
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.
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:O).
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 scope as set out in the accompanying claims.

Claims

An information recording material comprising a fluorine-containing nonionic surfactant, 1.5 X 10^-5 mol/m² or more of a polyvalent metal salt, and an anionic surfactant capable of forming a sparingly soluble salt, which has a solubility in water of 300mg/100g water (20°C) or less, 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 according to claim 1, wherein the fluorine-containing nonionic surfactant is selected from:
The information recording material according to claim 1, wherein the polyvalent metal salt is calcium nitrate, magnesium nitrate, barium sulfate or zinc stearate.
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).
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.
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.
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).
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.
The information recording material according to claim 1, wherein the information recording layer is a light-sensitive silver halide emulsion layer.
An information recording material according to claim 1 which represents a heat developable colour photographic light sensitive material comprising the fluorine-containing nonionic surfactant, the polyvalent metal salt and the anionic surfactant in a surface layer on the support on the side of a light sensitive silver halide emulsion layer.
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:
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.
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).
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.
The heat-developable color photographic light-sensitive material according to claim 14, wherein the polyvalent metal salt in the underlayer is calcium nitrate, magnesium nitrate, barium sulfate or zinc stearate.
The heat-developable color photographic light-sensitive material according to claim 14, 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).
The heat-developable color photographic light-sensitive material according to claim 14, 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.