Ionic compounds, compositions, functional materials, silver halide photographic light-sensitive materials, and diffusion transfer type silver halide photographic light-sensitive materials

Abstract

This invention provides an ionic compound having an anionic structure represented by Formula 1, as well as compositions comprising the above-mentioned ionic compound, functional materials, silver halide photographic materials, or diffusion transfer type silver halide photographic materials. In Formula 1, w represents an integer of 1 or more, x represents an integer of 2 or more, Si1 represents a substituent containing at least 3 or more Si atoms (two or more Si1 atoms may be the same or different), L1 represents a divalent linking group (two or more L1 atoms may be the same or different), and R represents a (x+w) valent organic group containing a carbon atom.

Description

Technical Field

[0001] This invention relates to an ionic compound, a composition, a functional material, a silver halide photographic material, and a diffusion-transfer type silver halide photographic material. Background Technology

[0002] To enhance user benefits in silver halide photographic photosensitive materials, significant increases in photosensitivity have been achieved in recent years. Furthermore, the manufacturing, imaging, and processing of silver halide photographic photosensitive materials have become increasingly high-speed and automated, requiring performance resistant to contact with various rollers or equipment, or to friction between photosensitive materials themselves. Photosensitive materials typically consist of an electrically insulating support and a photographic emulsion layer. Therefore, during the manufacturing process or use of photosensitive materials, static charge easily accumulates through contact, peeling, and friction with surfaces of the same or different types of substances.

[0003] Thus, if electrostatic charge accumulates before development, the photosensitive layer becomes photosensitive through the luminescence caused by the discharge of this charge. After development, this results in what is known as electrostatic haze. Furthermore, the accumulated electrostatic charge can also cause defects such as dust adhering to the photosensitive material.

[0004] As conventional silicon compounds, there are silicon compounds known, such as those described in Non-Patent Document 1, Non-Patent Document 2, or Patent Document 1.

[0005] Non-patent literature 1: Langmuir 2019, 35, 9785~9793

[0006] Non-patent literature 2: Phys. Chem. Chem. Phys., 2017, 19, 23869~23877

[0007] Patent Document 1: Japanese Patent Application Publication No. 6-25420 Summary of the Invention

[0008] The technical problem to be solved by the invention

[0009] The problem to be solved by the present invention is to provide a novel ionic compound.

[0010] Furthermore, another problem to be solved by the present invention is to provide a composition comprising the above-mentioned ionic compound, a functional material, a silver halide photographic material, or a diffusion transfer type silver halide photographic material.

[0011] means for solving technical problems

[0012] The means to solve the above problems include the following methods.

[0013] <1> An ionic compound having an anionic structure represented by the following formula 1.

[0014] [Chemical Formula 1]

[0015] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0016] <2> The ionic compound according to <1> is a compound represented by formula 2.

[0017] [Chemical Formula 2]

[0018] In Equation 2, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom. M 1 Indicates cations with valences of 1 to 3. n represents the relationship with M 1 Integers from 1 to 3 with equal valence.

[0019] <3> According to <1> or <2>, the ionic compound, wherein w is 1.

[0020] <4> According to <1> or <2>, the ionic compound wherein the anionic structure represented by Formula 1 above is a structure represented by any one of Formula a-1, Formula a-2 or Formula a-3 below.

[0021] [Chemical Formula 3]

[0022] In equations a-1 to a-3, Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. L A Indicates a single bond or a divalent linkage group. b represents 1 or 2. R B Represents a hydrogen atom or a hydrocarbon group. L B Indicates a single bond or a divalent linkage group, with two or more L... B They can be the same or different. Lc1 represents a single bond or a divalent linkage group. Two or more Lc1 groups can be the same or different. Lc2 represents a single bond or a divalent linkage group.

[0023] <5> According to <1> or <2>, the ionic compound is wherein the above-mentioned Si1 is a group represented by any one of the following formulas Si-1 to Si-4.

[0024] [Chemical Formula 4]

[0025] In formulas Si-1 to Si-4, R1 represents a hydrocarbon group; multiple R1 groups can be the same or different. y represents an integer greater than 2. R2 represents a hydrocarbon group; multiple R2 groups can be the same or different. z represents 2 or 3. R3 represents a hydrocarbon group; multiple R3 groups can be the same or different. p and q represent integers that satisfy p≥1, q≥1, and p+q≥3. R4, R 4a and R 4b Indicates a hydrocarbon group, multiple R4, R 4a and R 4b They can be the same or different. This indicates the bonding position with L1.

[0026] <6> A composition comprising: an ionic compound having an anionic structure represented by Formula 1 below; and an adhesive.

[0027] [Chemical Formula 5]

[0028] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0029] <7> A functional material having: a support; and a layer thereon, wherein the support contains an ionic compound having an anionic structure represented by Formula 1 below.

[0030] [Chemical Formula 6]

[0031] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0032] <8> A silver halide photographic material comprising: a support; and a layer thereon, wherein the support comprises an ionic compound having an anionic structure represented by the following formula 1.

[0033] [Chemical Formula 7]

[0034] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0035] <9> A diffusion transfer type silver halide photographic material, comprising: a support; and a layer, wherein the support contains an ionic compound having an anionic structure represented by the following formula 1.

[0036] [Chemical Formula 8]

[0037] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0038] Invention Effects

[0039] According to the present invention, a novel ionic compound can be provided.

[0040] Furthermore, according to the present invention, it is possible to provide a composition comprising the above-mentioned ionic compound, a functional material, a silver halide photographic material, or a diffusion transfer type silver halide photographic material. Detailed Implementation

[0041] The present invention will now be described in detail. The descriptions of the constituent elements described below are sometimes based on representative embodiments of the invention, but the invention is not limited to these embodiments.

[0042] In addition, in this specification, the "~" indicating a numerical range means that the values ​​recorded before and after it are included as the lower and upper limits.

[0043] In the numerical ranges described in stages in this invention, the upper or lower limit value described in one numerical range can be replaced with the upper or lower limit value of other numerical ranges described in stages. Furthermore, in the numerical ranges described in this invention, the upper or lower limit value of that numerical range can also be replaced with the values ​​shown in the embodiments.

[0044] Furthermore, in the designation of groups (atomic groups) in this specification, the designations without substitution and unsubstituted not only include groups without substituents but also groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl) but also alkyl groups with substituents (substituted alkyl).

[0045] In this specification, "(meth)acrylic acid" is a term used to encompass both acrylic acid and methacrylic acid, and "(meth)acryloyl" is a term used to encompass both acryloyl and methacryloyl.

[0046] Furthermore, the term "process" in this specification includes not only independent processes, but also processes that can achieve their intended purpose, even when they cannot be clearly distinguished from other processes. In this invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0047] Furthermore, in this invention, a combination of two or more preferred methods is a more preferred method.

[0048] Furthermore, unless otherwise stated, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this invention are values ​​determined by gel permeation chromatography (GPC).

[0049] In the GPC-based assay, the HLC (registered trademark)-8020GPC (manufactured by TOSOH CORPORATION) was used as the assay apparatus, three TSKgel (registered trademark) Super Multipore HZ-H (4.6mm ID × 15cm, manufactured by TOSOH CORPORATION) columns were used as the column, and THF (tetrahydrofuran) was used as the eluent. Furthermore, the assay conditions were set as follows: sample concentration of 0.45% by mass, flow rate of 0.35 ml / min, sample injection volume of 10 μL, and assay temperature of 40 °C. A differential refractive index (RI) detector was used.

[0050] The standard curve was prepared using eight samples from Tosoh Corporation's "Standard Samples TSK Standard, Polystyrene": "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", "A-1000" and "n-propylbenzene".

[0051] In this invention, "total solids content" refers to the total mass of the components after removing the solvent from all components of the composition. Furthermore, as mentioned above, "solids content" refers to the components after removing the solvent, which may be solid or liquid at 25°C.

[0052] The present invention will now be described in detail.

[0053] (Ionic compounds)

[0054] The ionic compounds involved in this invention are ionic compounds having anionic structures represented by the following Formula 1.

[0055] [Chemical Formula 9]

[0056] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0057] The ionic compounds involved in this invention have a specific branched structure represented by Formula 1 above and an anionic structure with sulfonic acid groups, and are novel compounds.

[0058] Furthermore, when the ionic compounds involved in this invention are used for film or layer formation, the coating surface is also excellent.

[0059] From the viewpoint of water solubility and surface activity, w in Formula 1 is preferably an integer from 1 to 8, more preferably an integer from 1 to 4, even more preferably 1 or 2, and especially preferably 1.

[0060] From the viewpoint of water solubility and surface activity, x in Formula 1 is preferably an integer from 2 to 8, more preferably an integer from 2 to 4, even more preferably 2 or 3, and especially preferably 2.

[0061] From the viewpoint of water solubility and surface activity, the number of Si atoms in Sil1 in Formula 1 is preferably an integer from 3 to 20, more preferably an integer from 3 to 12, even more preferably an integer from 3 to 10, and especially preferably an integer from 4 to 7.

[0062] The aforementioned Sil1 is preferably bonded to Si atoms via L1.

[0063] There are no particular restrictions on the substituents on the Si atoms in the above-mentioned Sil1, but from the viewpoint of water solubility and surface activity, the substituents other than silyl or siloxy groups are preferred to be hydrocarbon groups or alkoxy groups, and more preferably hydrocarbon groups.

[0064] From the viewpoint of water solubility and surface activity, the aforementioned hydrocarbon group is preferably an alkyl group with 1 to 6 carbon atoms, more preferably methyl, ethyl, or branched alkyl groups with 3 to 6 carbon atoms, and even more preferably tert-butyl or methyl, especially methyl.

[0065] Furthermore, the presence of multiple Sil1 molecules preferably indicates the presence of the same functional group.

[0066] From the viewpoint of water solubility and surface activity, the above-mentioned Si1 is preferably a group represented by any one of the following formulas Si-1 to Si-4, and more preferably a group represented by any one of the following formulas Si-3 or Si-4.

[0067] [Chemical Formula 10]

[0068] In formulas Si-1 to Si-4, R1 represents a hydrocarbon group; multiple R1 groups can be the same or different. y represents an integer greater than 2. R2 represents a hydrocarbon group; multiple R2 groups can be the same or different. z represents 2 or 3. R3 represents a hydrocarbon group; multiple R3 groups can be the same or different. p and q represent integers that satisfy p≥1, q≥1, and p+q≥3. R4, R 4a and R 4b Indicates a hydrocarbon group, multiple R4, R 4a and R 4b They can be the same or different. This indicates the bonding position with L1.

[0069] As R1~R4, R 4a and R 4b From the viewpoint of water solubility and surface activity, the hydrocarbon group in the form is preferably an alkyl group with 1 to 6 carbon atoms, more preferably methyl, ethyl or branched alkyl with 3 to 6 carbon atoms, further preferably tert-butyl or methyl, and especially preferably methyl.

[0070] Furthermore, the multiple R1 to R4 are preferably the same group.

[0071] Moreover, when there are multiple R 4a or R 4b In the case of [the specific group], it is preferable to use the same group.

[0072] In formula Si-2, y is preferably an integer from 2 to 50, more preferably an integer from 2 to 20, even more preferably from 2 to 10, and especially preferably 2.

[0073] From the perspective of water solubility and surface activity, z in formula Si-3 is preferably 2.

[0074] From the perspective of water solubility and surface activity, p in formula Si-4 is preferably 1 or 2.

[0075] From the perspective of water solubility and surface activity, q in formula Si-4 is preferably 1 or 2.

[0076] Furthermore, from the viewpoint of water solubility and surface activity, the above-mentioned p and q are preferably integers that satisfy p+q=3 or p+q=4.

[0077] From the viewpoint of water solubility and surface activity, L1 in Formula 1 is preferably an alkylene group or a group formed by bonding an alkylene group with a polyalkoxide group, more preferably an alkylene group or a group formed by bonding an alkylene group with a polyethoxy group, and especially preferably an alkylene group.

[0078] The aforementioned alkylene group is more preferably an alkylene group having 2 to 10 carbon atoms, further preferably an alkylene group having 2 to 4 carbon atoms, and especially preferably an alkylene group having 2 or 3 carbon atoms.

[0079] Furthermore, the presence of multiple L1s preferably indicates the presence of the same group.

[0080] From the viewpoint of water solubility and surface activity, the number of carbons in R in Formula 1 is preferably 2 to 20, more preferably 3 to 15, even more preferably 4 to 10, and especially preferably 4 to 6.

[0081] Furthermore, from the viewpoint of water solubility and surface activity, R in Formula 1 is preferably a group having an oxygen atom, more preferably a group having at least one type of bond selected from the group consisting of ester bonds and ether bonds, even more preferably a group having at least one type of bond selected from the group consisting of two or more ester bonds and ether bonds, and especially preferably a group having at least one type of bond selected from the group consisting of two or more and twelve or fewer ester bonds and ether bonds.

[0082] Furthermore, from the viewpoint of water solubility and surface activity, R in Formula 1 is preferably the group shown below.

[0083] [Chemical Formula 11]

[0084] In the above groups, # indicates the bonding position with L1, and ## indicates the bonding position with SO3. - The bonding positions.

[0085] From the viewpoint of water solubility and surface activity, the anionic structure represented by Formula 1 above is preferably represented by any one of Formula a-1, Formula a-2 or Formula a-3 below, more preferably by Formula a-1 or Formula a-2 below, and especially preferably by Formula a-1 below.

[0086] [Chemical Formula 12]

[0087] In equations a-1 to a-3, Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. L A Indicates a single bond or a divalent linkage group. b represents 1 or 2. R B Represents a hydrogen atom or a hydrocarbon group. L B Indicates a single bond or a divalent linkage group, with two or more L... B They can be the same or different. Lc1 represents a single bond or a divalent linkage group. Two or more Lc1 groups can be the same or different. Lc2 represents a single bond or a divalent linkage group.

[0088] In equations a-1 to a-3, Sil1 and L1 have the same meaning as Sil1 and L1 in equation 1, and their preferred methods are also the same.

[0089] L in equation a-1 A Preferably, it is a single bond or an alkylene group, more preferably a single bond or a methylene group, and especially preferably a single bond.

[0090] From the perspective of water solubility and surface activity, b in formula a-1 is preferably 1.

[0091] R in equation a-2 B Preferably, it is a hydrogen atom or an alkyl group, more preferably a hydrogen atom, methyl or ethyl group, and especially preferably a hydrogen atom.

[0092] L in equation a-2 B Each is preferably a single bond or an alkylene group, more preferably a single bond or a methylene group.

[0093] In formula a-3, Lc1 is preferably a single bond or an alkylene bond, more preferably a single bond.

[0094] In formula a-3, Lc2 is preferably a single bond or an alkylene group, more preferably a single bond.

[0095] The ionic compounds involved in this invention have counter-cations.

[0096] The counter cation can be any of the following: a metal cation, ammonium, or other organic cations. However, a metal cation is preferred, more preferably a divalent or monovalent metal cation, and even more preferably a monovalent metal cation, especially Na. + or K + .

[0097] Furthermore, alkali metal ions, alkaline earth metal ions, and Al are preferred as counter cations. 3+ Fe 2+ Fe 3+Or primary ammonium cations to quaternary ammonium cations, more preferably alkali metal ions or alkaline earth metal ions, especially alkali metal ions.

[0098] Examples of alkali metals include lithium (Li), sodium (Na), potassium (K), and cesium (Cs).

[0099] Examples of alkaline earth metals include calcium (Ca), strontium (Sr), and barium (Ba).

[0100] From the viewpoint of water solubility and surface activity, the ionic compound involved in this invention is preferably a compound represented by Formula 2.

[0101] [Chemical Formula 13]

[0102] In Equation 2, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom. M 1 Indicates cations with valences of 1 to 3. n represents the relationship with M 1 Integers from 1 to 3 with equal valence.

[0103] In Equation 2, w, x, Sil1, L1 and R have the same meanings as w, x, Sil1, L1 and R in Equation 1, and the preferred methods are also the same.

[0104] M in Equation 2 1 Preferably, it is a monovalent to trivalent metal cation or a primary ammonium cation to a quaternary ammonium cation, more preferably a divalent or monovalent metal cation, even more preferably a monovalent metal cation, and especially preferably Na. + or K + .

[0105] In Formula 2, n is preferably 1 or 2, and more preferably 1.

[0106] Specific examples of anionic structures represented by Formula 1 include A1-1 to A1-14, A2-1 to A2-8, A3-1, A3-2, and A4-1. Additionally, Me represents a methyl group.

[0107] As a specific example of the ionic compound involved in this invention, preferred examples include compounds having any one of the following anionic structures: A1-1 to A1-14, A2-1 to A2-8, A3-1, A3-2, and A4-1, and Na. + K + Cs + Mg 2+ Fe 3+ Or tetramethylammonium as a compound to counteract cations.

[0108] Furthermore, in the following description, for example, sodium salts of Al-1 are sometimes referred to as Al-1Na, etc.

[0109] [Chemical Formula 14]

[0110] [Chemical Formula 15]

[0111] <Uses>

[0112] The use of the ionic compounds involved in this invention is not particularly limited, and they can preferably be used as leveling agents or surfactants.

[0113] Furthermore, the ionic compounds involved in this invention can be preferably used in known applications involving leveling agents or surfactants.

[0114] Moreover, the ionic compounds involved in this invention can preferably be used for film formation.

[0115] Furthermore, the ionic compounds involved in this invention can be preferably used in photosensitive materials, surface modifiers, compositions for forming protective layers, compositions for forming conductive layers, compositions for forming base layers, pressure-responsive materials, heat-responsive materials, microcapsules, microgels, etc.

[0116] The ionic compounds involved in this invention are particularly preferred for use in silver halide photographic materials and diffusion transfer type silver halide photographic materials.

[0117] (Composition)

[0118] The compositions involved in this invention comprise an ionic compound having an anionic structure represented by Formula 1 below (the ionic compound involved in this invention) and an adhesive.

[0119] [Chemical Formula 16]

[0120] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0121] The preferred embodiment of the ionic compound in the composition of the present invention is the same as the preferred embodiment of the ionic compound of the present invention described above.

[0122] In the compositions involved in this invention, the ionic compound involved in this invention may contain one or more types.

[0123] The content of the ionic compound involved in the present invention in the composition can be appropriately selected according to its use. It is preferably 0.0001% to 50% by mass, more preferably 0.001% to 20% by mass, and especially preferably 0.01% to 10% by mass relative to the total solid content of the composition.

[0124] <Adhesive>

[0125] The compositions involved in this invention comprise adhesives.

[0126] As an adhesive, there are no particular restrictions; it can be selected appropriately according to the application. Furthermore, known adhesive polymers and known monomers (polymeric compounds) can be used.

[0127] Examples of adhesive polymers include, for example, epoxy resins, diallyl phthalate resins, silicone resins, phenolic resins, unsaturated polyester resins, polyimide resins, polyurethane resins, melamine resins, urea-formaldehyde resins, ionomer resins, ethylene ethyl acrylate resins, acrylonitrile-acrylate-styrene copolymer resins, acrylonitrile-styrene resins, acrylonitrile-chlorinated polyethylene-styrene copolymer resins, ethylene-vinyl acetate resins, ethylene-vinyl alcohol copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, vinyl chloride resins, chlorinated polyethylene resins, polyvinylidene chloride resins, cellulose acetate resins, and fluorinated polymers. Resins, polyoxymethylene resins, polyamide resins, polyarylate resins, thermoplastic polyurethane elastomers, polyetheretherketone resins, polyethersulfone resins, polyethylene, polypropylene, polycarbonate resins, polystyrene, polystyrene-maleic acid copolymer resins, polystyrene-acrylic acid copolymer resins, polyphenylene ether resins, polyphenylene sulfide resins, polybutadiene resins, polybutylene terephthalate resins, acrylic resins, methacrylic acid resins, methylpentene resins, polylactic acid, polybutylene succinate resins, butyral resins, formalin resins, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and their copolymers.

[0128] Examples of polymerizable compounds (monomers) include (meth)acrylic acid monomers, epoxy monomers, oxocyclobutyl monomers, and ethylene monomers.

[0129] There are no particular limitations on (meth)acrylic acid monomers; well-known examples include (meth)acrylate compounds, (meth)acrylamide compounds, (meth)acrylic acid, and (meth)acrylonitrile.

[0130] Specifically, examples include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, and ethylhexyl methacrylate; hydroxyalkyl methacrylates such as methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, hydroxypentyl methacrylate, and hydroxyhexyl methacrylate; and dimethylaminoethyl methacrylate. Alkylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, and other alkylaminoalkyl methacrylates; benzyl methacrylate, phenoxyethyl methacrylate, and other aromatic ring-containing methacrylates; styrene, α-methylstyrene, chlorostyrene, and other styrene derivatives; cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, cyclononyl methacrylate, cyclodecyl methacrylate, isobornyl methacrylate, norbornyl methacrylate, and other alkylaminoalkyl methacrylates. Alicyclic (meth)acrylates such as adamantane acrylate, dicyclopentyl (meth)acrylate, and dicyclopentenoxyethyl (meth)acrylate; N-hydroxyalkyl (meth)acrylamides such as N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and N-hydroxybutyl (meth)acrylamide; and N-alkoxyalkyl (meth)acrylamides such as N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-(n-, iso)butoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, and N-(n-, iso)butoxyethyl (meth)acrylamide. (Meth)acrylamide, (meth)acrylonitrile, tricyclodecanediethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane triacrylate, trimethylolpropane PO (propylene oxide) modified triacrylate, trimethylolpropane EO (ethylene oxide) modified triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc.

[0131] Examples of epoxy monomers, i.e., monomers containing epoxy groups, include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenolic varnish type epoxy resin, o-cresol phenolic varnish type epoxy resin, trihydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadienol type epoxy resin, hydrogenated bisphenol A type epoxy resin, polyol type epoxy resin containing a bisphenol A core, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glyoxal type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, etc.

[0132] The compositions involved in this invention may contain one type of adhesive alone, or two or more types.

[0133] The content of the adhesive in the composition involved in this invention can be appropriately selected according to its use. It is preferably 1% to 99% by mass, more preferably 5% to 90% by mass, and especially preferably 10% to 80% by mass relative to the total solid content of the composition.

[0134] Furthermore, when the composition according to the present invention contains other additives, such as those described later, in addition to the adhesive, it is sufficient to contain an adhesive in a proportion sufficient to form the desired functional film. In this case, the content of the adhesive relative to the total solids content of the composition is preferably 0.5% to 98% by mass, more preferably 2% to 60% by mass, and may also be 2% to 50% by mass.

[0135] <Polymerization Initiator>

[0136] The compositions involved in this invention may contain a polymerization initiator.

[0137] In the case of containing the above-mentioned polymerizable compound, a polymerization initiator is preferably included.

[0138] Examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators.

[0139] Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators.

[0140] Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaaryl biimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds, etc.

[0141] Examples of thermal polymerization initiators include diazo compounds, peroxides, and onium salts.

[0142] The compositions involved in this invention may contain one polymerization initiator alone, or two or more.

[0143] The content of the polymerization initiator in the composition involved in this invention can be appropriately selected according to its use. It is preferably 0.1% to 30% by mass, more preferably 0.5% to 25% by mass, and especially preferably 1% to 20% by mass, relative to the total solid content of the composition.

[0144] <Curing agent>

[0145] The compositions involved in this invention may contain a curing agent.

[0146] For example, examples of curing agents for resins containing hydroxyl groups include polyisocyanates, partial condensates of isocyanate compounds, adducts with polymers or polyols, low molecular weight polyester films, end-capped polyisocyanate compounds with isocyanate groups capped by end-capping agents such as phenol, melamine resins, urea resins, polybasic acids or their anhydrides, etc. Furthermore, examples of curing agents for resins containing epoxy groups include aliphatic polyamines, aromatic polyamines, polyamide amines, modified polyamines, polythiols, anhydrides, phenolic resins, phenolic varnishes, etc.

[0147] <Solvent>

[0148] From the viewpoint of coatability, the compositions involved in this invention may contain solvents.

[0149] Examples of solvents include water, organic solvents, and mixtures of water and organic solvents.

[0150] As water, it can be distilled water, ion-exchanged water, etc.

[0151] Organic solvents can be appropriately selected according to the intended use or purpose of the liquid composition. Examples of organic solvents include esters, ethers, ketones, aromatic hydrocarbons, and alcohols.

[0152] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetic acid esters (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionate esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and alkyl 2-oxypropionate esters). Alkyl ester solvents of 2-oxy-2-methylpropionate (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; specifically, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, cyclohexyl acetate, and 1-methyl-2-methoxyethyl propionate.)

[0153] Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as PEGMEA), diethylene glycol monoethyl ether acetate (also known as ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

[0154] Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

[0155] Examples of aromatic hydrocarbons include, for example, toluene and xylene.

[0156] Examples of alcohols include monohydric alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol, pentanediol, glycerol, hexanetriol, thiodiglycol), and diol derivatives (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monophenyl ether), etc.

[0157] Furthermore, from the viewpoint of further enhancing leveling or surface activity, at least one solvent selected from the group consisting of water and water-soluble solvents can be preferred as a solvent.

[0158] In addition to the substances exemplified in the alcohols mentioned above, other water-soluble solvents include amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine), and other polar solvents (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidinone, 1,3-dimethyl-2-imidazolinone, acetonitrile, acetone), etc.

[0159] The compositions involved in this invention may contain one solvent alone or two or more solvents.

[0160] The solvent content in the composition involved in this invention can be appropriately selected according to its intended use.

[0161] <Other Additives>

[0162] In addition to the above-mentioned components, the compositions involved in this invention may also contain known additives depending on their intended use.

[0163] Other additives include, for example, colorants, surfactants other than the ionic compounds involved in this invention, leveling agents other than the ionic compounds involved in this invention, fillers, anti-fading agents, emulsion stabilizers, penetration promoters, ultraviolet absorbers, preservatives, mildew inhibitors, pH adjusters, viscosity adjusters, dispersion stabilizers, rust inhibitors, chelating agents, and other known additives.

[0164] (Functional materials)

[0165] The functional material of the present invention has a support and a layer thereon comprising an ionic compound having an anionic structure represented by the following Formula 1 (the ionic compound of the present invention).

[0166] [Chemical Formula 17]

[0167] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0168] As for the functional materials involved in this invention, there are no particular limitations as long as the support has a layer containing the ionic compound involved in this invention, but photosensitive materials, materials with a protective layer, materials with a conductive layer, materials with a base layer, pressure-responsive materials, and heat-responsive materials are preferred examples.

[0169] Among them, silver halide photographic materials and diffusion transfer type silver halide photographic materials, which are described later, are particularly preferred.

[0170] <Layer containing the ionic compound involved in this invention>

[0171] The preferred embodiment of the ionic compound in the functional material involved in this invention is the same as the preferred embodiment of the ionic compound involved in this invention described above.

[0172] The functional materials involved in this invention may contain only one ionic compound involved in this invention, or may contain two or more.

[0173] The layer containing the ionic compound involved in this invention can be a single layer or multiple layers. When the functional material is formed of multiple layers, these layers can be formed sequentially or by simultaneous multilayer coating or the like.

[0174] The content of the ionic compound involved in the present invention in the above-mentioned layer of the functional material involved in the present invention can be appropriately selected according to its use. Relative to the total mass of the above-mentioned layer, it is preferably 0.0001% to 50% by mass, more preferably 0.001% to 20% by mass, and especially preferably 0.01% to 10% by mass.

[0175] Depending on its intended use, the aforementioned layer may contain known components. For example, it may contain the aforementioned adhesive, the aforementioned polymerization initiator, as well as colorants, surfactants other than the ionic compounds involved in this invention, leveling agents other than the ionic compounds involved in this invention, fillers, anti-fading agents, emulsion stabilizers, penetration promoters, ultraviolet absorbers, preservatives, mildew inhibitors, pH adjusters, viscosity adjusters, dispersion stabilizers, rust inhibitors, chelating agents, etc.

[0176] Furthermore, it may also contain various components found in silver halide photographic materials or diffusion transfer type silver halide photographic materials, as described later.

[0177] There is no particular limitation on the average thickness of the above-mentioned layers, which can be selected according to the application, but it is preferably 0.01μm to 1mm, and more preferably 0.1μm to 200μm.

[0178] Furthermore, in this invention, the method for measuring the average thickness is as follows.

[0179] The sample is cut on a surface parallel to the thickness direction, and the thickness is measured at more than 5 points in the cross section. The average value of these measurements is taken as the average thickness.

[0180] The ionic compounds involved in this invention are particularly effective in preventing pinholes or improving surface texture when the outermost layer of a functional material has a matting agent that is larger than the average film thickness of the layer. Specifically, the ratio of the particle size D of the matting agent to the average film thickness d (D / d) is preferably 1.5 to 60, more preferably 5 to 50, and even more preferably 10 to 50. The content of the matting agent varies depending on the desired surface shape, but is preferably 10 mg / m². 2 ~800mg / m 2 More preferably 20 mg / m 2 ~600mg / m 2 More preferably 30 mg / m 2 ~500mg / m 2 In this case, the adhesive is preferably a water-soluble colloid, such as gelatin, carboxymethyl cellulose, polyvinyl alcohol, etc.

[0181] <Suitable silicone surfactants>

[0182] The functional materials involved in this invention can use silicone-based surfactants as shown below. Silicone-based surfactants refer to surfactants with a polysiloxane structure, which may have functional groups such as polyether modified groups, polyether-alkyl co-modified groups, polyglycerol modified groups, and polyglycerol-alkyl co-modified groups, as well as hydrophilic groups, and hydrophilic polymer chains in their side chains, ends, etc. More specifically, it is preferable to include silicone-based surfactants represented by the following general formula (1).

[0183] [Chemical Formula 18]

[0184] In formula (1), m is an integer of 1 or more and 200 or less, preferably 2 or more and 100 or less, more preferably 5 or more and 50 or less; n is an integer of 1 or more and 100 or less, preferably 2 or more and 80 or less, more preferably 4 or more and 50 or less. In formula (1), a is an integer of 0 or more and 40 or less, preferably 35 or less, more preferably 25 or less, and even more preferably 15 or less; b is an integer of 0 or more and 40 or less, preferably 2 or more and 35 or less, more preferably 4 or more and 25 or less, and even more preferably 6 or more and 20 or less.

[0185] (a+b) is preferably 1 or more and 50 or less, more preferably 2 or more and 40 or less, and even more preferably 5 or more and 30 or less. In addition, each structural unit of m, n, a and b can be a block copolymer or a random copolymer.

[0186] From the viewpoint of the drying properties of the coating composition, the ratio of m to n (m / n) is preferably 1.5 or more and 20 or less, more preferably 1.8 or more and 15 or less, and even more preferably 2.0 or more and 10 or less. This ratio (m / n) is determined by proton nuclear magnetic resonance (NMR)... 1 H-NMR (H-NMR) spectrophotometry is used to calculate the ratio of modified Si to unmodified Si.

[0187] From the viewpoint of improving the wetting and spreading properties of the coating composition, the [(a+b) / (m / n)] ratio is preferably 1.6 or more and 6.3 or less, more preferably 1.7 or more and 5.5 or less, and even more preferably 1.8 or more and 5.0 or less.

[0188] In general formula (1), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0189] Examples of polyether-modified silicone surfactants represented by general formula (1) include PEG-3 dimethylsiloxane, PEG-9 dimethylsiloxane, PEG-9 methyl ether dimethylsiloxane, PEG-10 dimethylsiloxane, PEG-11 methyl ether dimethylsiloxane, PEG / PPG-20 / 22 butyl ether dimethylsiloxane, PEG-32 methyl ether dimethylsiloxane, PEG-9 polydimethylsiloxoethyl dimethylsiloxane, lauryl PEG-9 polydimethylsiloxoethyl dimethylsiloxane, PEG-9 dimethylsiloxane, and (PEG-15 / lauryl polydimethylsiloxoethyl dimethylsiloxane) crosslinked polymers.

[0190] Commercially available silicone surfactants include, for example, BYK-302, BYK-306, BYK-307, BYK-326, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-379, BYK-3451, BYK-3565, and BYK-UV3530 (these are trade names, BYK Japan). KK.Manufactured), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-618, KF-642, KF-64 3. KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6013, K F-6015, KF-6017, KF-6028, KF-6038, KF-6043, KP-101, KP-104, KP-105, KP-106, KP-109 , KP-110, KP-112, KP-118, KP-120, KP-121, KP-124, KP-125, KP-341 (the above are trade names, Shin-Etsu SAG503A, SAG014 (the above are trade names, manufactured by Nissin Chemical Co., Ltd.), TEGO WET240, TEGO WET270 (the above are trade names, manufactured by Evonik Industries AG), EMALEX-SS-5602, SS-1906EX (the above are trade names, manufactured by NIHON EMULSION Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (the above are trade names, manufactured by Dow Corning Toray Co., Ltd.), BYK-33, BYK-387 (the above are trade names, manufactured by BYK Japan KK.), TSF4440, TSF4452, TSF4453 (the above are trade names, manufactured by Toshiba Silicone). Co., Ltd., etc.

[0191] <Support>

[0192] The functional material involved in this invention has a support.

[0193] Examples of supports include metal plates, glass plates, resin plates, resin films, paper supports, or metal foils. Furthermore, they can be laminates with various functional layers.

[0194] Furthermore, the support can undergo surface treatment.

[0195] There is no particular limitation on the average thickness of the support, but it is preferably 0.1 μm or more and 10 cm or less, and more preferably 1 μm or more and 1 mm or less.

[0196] <Other Layers>

[0197] The functional material involved in this invention may have other layers between the support and the above-mentioned layers, or on the side of the support opposite to the side having the above-mentioned layers, depending on the application.

[0198] There are no particular restrictions on other layers; examples of well-known layers in commonly known uses can be cited.

[0199] (Silver halide photographic materials)

[0200] The silver halide photographic material of the present invention has a support and a layer comprising an ionic compound having an anionic structure represented by the following Formula 1 (the ionic compound of the present invention).

[0201] [Chemical Formula 19]

[0202] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0203] Silver halide photographic photosensitive materials are preferably materials that are photosensitive to light, laser or X-ray irradiation. For example, they are preferably selected from black and white reversal film, black and white negative film, color reversal film, color negative film, film in which photosensitive photographic components are digitally scanned, black and white reversal photographic paper, black and white photographic paper, color photographic paper, reversal color photographic paper, photographic paper in which photosensitive photographic components are photosensitive from a digital database by laser irradiation, and photosensitive materials that are developed by heat.

[0204] The preferred embodiment of the ionic compound in the silver halide photographic material of the present invention is the same as the preferred embodiment of the ionic compound of the present invention described above.

[0205] In the silver halide photographic photosensitive material involved in this invention, the ionic compound involved in this invention may contain one type alone, or two or more types.

[0206] The content of the ionic compound involved in the present invention in the above-mentioned layer of the silver halide photographic photosensitive material involved in the present invention can be appropriately selected according to its use. Relative to the total mass of the above-mentioned layer, it is preferably 0.0001% to 50% by mass, more preferably 0.001% to 20% by mass, and especially preferably 0.01% to 10% by mass.

[0207] The aforementioned layer can be any layer constituting the silver halide photographic material described later. When forming a layer by coating, it is preferably the outermost layer during coating. When multiple layers are stacked sequentially, it is preferable to use each layer as the outermost layer in the sequential coating process.

[0208] Furthermore, in the silver halide photographic material involved in this invention, the layer containing the ionic compound involved in this invention can be one layer or two or more layers.

[0209] The aforementioned layer may contain various components found in silver halide photographic materials, as described later.

[0210] In this invention, when the ionic compound of this invention is used in the layer of a photographic photosensitive material, the aqueous coating composition containing the ionic compound of this invention may consist only of the ionic compound of this invention and water, or may appropriately contain other components depending on the purpose.

[0211] In the above-mentioned aqueous coating composition, the ionic compound involved in the present invention may be used only one type, or two or more types may be used in combination.

[0212] Furthermore, surfactants other than the ionic compounds involved in this invention can be used together with the ionic compounds involved in this invention.

[0213] Various anionic, cationic, and nonionic surfactants can be used, including polymeric surfactants and silicone surfactants other than the ionic compounds involved in this invention. Anionic or nonionic surfactants are more preferred. Specifically, compounds that can be used in the functional materials involved in this invention can be cited. Furthermore, when the target is a photosensitive material, nonionic silicone surfactants containing epoxy alkyl groups are particularly preferred because they exhibit less reduction in photosensitivity during storage, and less mordant inhibition, especially in diffusion transfer type silver halide photographic photosensitive materials.

[0214] Examples of surfactants that can be used together include Japanese Patent Application Publication No. 62-215272 (pp. 649-706), Research Disclosure (RD) Item 17643, pp. 26-27 (December 1978), Research Disclosure (RD) Item 18716, pp. 650 (November 1979), and Research Disclosure (RD) Item 307105, pp. 875-876 (November 1989).

[0215] Representative substances that can be included in the above-mentioned aqueous coating compositions are polymer compounds. The polymer compound can be a polymer soluble in a water-soluble solvent (soluble polymer) or an aqueous dispersion of a polymer (so-called polymer latex).

[0216] There are no particular limitations on soluble polymers, and examples include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, etc. As polymer latexes, examples include homopolymers or copolymers of various vinyl monomers (e.g., acrylate derivatives, methacrylate derivatives, acrylamide derivatives, methacrylamide derivatives, styrene derivatives, conjugated diene derivatives, N-vinyl compounds, O-vinyl compounds, vinyl nitrile, other vinyl compounds (e.g., ethylene, vinylidene chloride)) and dispersions of condensation polymers (e.g., polyester, polyurethane, polycarbonate, polyamide). Detailed examples of such polymer compounds can be found in, for example, Japanese Patent Application Publication No. 62-215272 (pp. 707-763), or Research Disclosure (RD) Item 17643, p. 651 (December 1978), Research Disclosure (RD) Item 18716, p. 650 (November 1979), Research Disclosure (RD) Item 307105, p. 873-874 (November 1989), etc.

[0217] The solvent in the above-mentioned aqueous coating composition can be water alone, or it can be a mixture of water and an organic solvent other than water (e.g., methanol, ethanol, isopropanol, n-butanol, methyl cellosolve, dimethylformamide, acetone, ethyl acetate, etc.). The proportion of water in the solvent of the aqueous coating composition is preferably 50% by mass or more.

[0218] In the above-described aqueous coating composition, various compounds may be included depending on the layer of the photographic photosensitive material used, and these compounds can be dissolved in the medium or dispersed. Examples of these include various colorants, ultraviolet absorbers, anti-color mixing agents, antistatic agents, cleaning agents, anti-fogging agents, hardening agents, dyes, and anti-mildew agents. Furthermore, in order to obtain effective antistatic properties and coating uniformity when used in photographic photosensitive materials, a hydrophilic colloidal layer is preferred as the outermost layer.

[0219] In this case, the coating composition of the above-mentioned layer may contain other surfactants, matting agents, lubricants, colloidal silica, plasticizers, etc., in addition to hydrophilic colloids (e.g., gelatin) and ionic compounds involved in the present invention.

[0220] There is no particular limitation on the amount of the ionic compound used in this invention, and its amount can be arbitrarily changed according to the structure of the ionic compound or its use, the type or amount of the compound contained in the aqueous composition, the structure of the solvent, etc., according to this invention. For example, when the ionic compound of this invention is used as a coating solution for the uppermost hydrophilic colloidal (gelatin) layer of the photographic photosensitive material, which is a preferred embodiment of this invention, the concentration in the coating solution is preferably 0.003% to 0.5% by mass, and preferably 0.03% to 10% by mass relative to the solid content of gelatin.

[0221] In this invention, when the photographic photosensitive material has a layer formed of a hydrophobic binder component, the ionic compound and the hydrophobic binder component described in this invention can be used together with an organic solvent in the composition used to make the layer. The preferred method in this case is the same as the preferred method for a layer containing the ionic compound described in this invention.

[0222] The silver halide photographic photosensitive material involved in this invention only requires that at least one photosensitive layer be provided on the support.

[0223] A typical example is a silver halide photographic photosensitive material having at least one photosensitive layer on a support, consisting of multiple silver halide emulsion layers with substantially the same color sensitivity but different photosensitivity. This photosensitive layer is a unit photosensitive layer sensitive to any one of blue, green, and red light. In multilayer silver halide color photographic photosensitive materials, the unit photosensitive layers are typically arranged sequentially from the support side in the order of red, green, and blue colorsensitive layers. However, depending on the purpose, the above arrangement order can be reversed, and different photosensitive layers can also be used, such as interspersed within the same colorsensitive layer. Non-photosensitive layers can be provided between the aforementioned silver halide photosensitive layers, as well as at the top and bottom layers. These may include color-forming agents, DIR compounds, anti-mixing agents, etc., as described later. As described in DE1,121,470 or GB923,045, the multiple silver halide emulsion layers constituting each unit photosensitive layer are preferably arranged such that the high-sensitivity emulsion layer and the low-sensitivity emulsion layer decrease in sensitivity toward the support. Furthermore, as described in Japanese Patent Application Publications Nos. 57-112751, 62-200350, 62-206541, and 62-206543, a low-sensitivity emulsion layer can be provided on the side away from the support, and a high-sensitivity emulsion layer can be provided on the side closer to the support.

[0224] As a specific example, the layers can be arranged sequentially from the side furthest from the support in the following order: low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / high sensitivity red photosensitive layer (RH) / low sensitivity red photosensitive layer (RL), BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH, etc.

[0225] Furthermore, as described in Japanese Patent Publication No. 55-34932, the layers can be arranged in the order of blue photosensitive layer / GH / RH / GL / RL from the side furthest from the support. Furthermore, as described in Japanese Patent Application Publication Nos. 56-25738 and 62-63936, the layers can also be arranged in the order of blue photosensitive layer / GL / RL / GH / RH from the side furthest from the support. Furthermore, as described in Japanese Patent Publication No. 49-15495, an arrangement can be given as follows: the upper layer is a silver halide emulsion layer with the highest photosensitivity, the middle layer is a silver halide emulsion layer with lower photosensitivity, and the lower layer is a silver halide emulsion layer with even lower photosensitivity than the middle layer, and it consists of three layers with different photosensitivity decreasing towards the support. Even in the case of a three-layer structure with different photosensitivity, as described in Japanese Patent Application Publication No. 59-202464, a medium-sensitivity emulsion layer, a high-sensitivity emulsion layer, and a low-sensitivity emulsion layer can be sequentially arranged from the side furthest from the support in the same color-sensitive layer.

[0226] Alternatively, a high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer or a low-sensitivity emulsion layer / medium-sensitivity emulsion layer / high-sensitivity emulsion layer can be configured sequentially. Furthermore, when there are four or more layers, the arrangement can be changed as described above. To improve color reproduction, it is preferable to arrange the main photosensitive layers (BL, GL, RL, etc.) and donor layers (CL) with different spectral sensitivity distributions, as described in U.S. Patent Nos. 4,663,271, 4,705,744, 4,707,436, Japanese Patent Application Publication Nos. 62-160448, and 63-89850, adjacent to or close to the main photosensitive layer.

[0227] The preferred silver halide used in this invention is silver iodide bromide, silver iodide chloride, or silver iodide chlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred are silver iodide bromide or silver iodide chlorobromide containing about 2 mol% to about 10 mol% of silver iodide.

[0228] Silver halide particles in photographic emulsions can be regular crystals such as cubic, octahedral, or tetrahedral, irregular crystals such as spherical or flattened, crystal defects such as twinning, or complexes thereof. The particle size of silver halide can be less than approximately 0.2 μm, or large particles with a projected area diameter up to approximately 10 μm. They can be polydisperse or monodisperse emulsions.

[0229] The silver halide photographic emulsions that can be used in this invention include, for example, Research Disclosure (hereinafter referred to as RD) No. 17643 (December 1978), pp. 22-23, “I. Emulsion preparation and types”; Research Disclosure No. 18716 (November 1979), p. 648; Research Disclosure No. 307105 (November 1989), pp. 863-865; Glafkides, “The Physics and Chemistry of Photography”, Paul Montel (P. Glafkides, Chimie et Physique Photographiques, Paul Montel, 1967); Duffin, “The Chemistry of Photographic Emulsions”, Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966); and Zelikman et al., “The Preparation and Coating of Photographic Emulsions”, Focal Press (VL Zelikman, et al.). Prepared using the methods described in (e.g., Making and Coating Photographic Emulsion, Focal Press, 1964).

[0230] Monodisperse emulsions as described in U.S. Patent No. 3,574,628, U.S. Patent No. 3,655,394, and GB 1,413,748 are also preferred. Furthermore, plate-shaped particles with an aspect ratio of about 3 or higher can also be used in this invention. In particular, to improve shelf life, emulsions in which at least 50% of the total projected area is occupied by silver halide plate-shaped particles with an aspect ratio of 8 or higher are preferred. There is no particular upper limit to the aspect ratio, but 30 or less is preferred. The plate-shaped particles can be readily prepared by the methods described in Gutoff, *Photographic Science and Engineering*, Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520, and GB 2,112,157.

[0231] The crystal structure can be homogeneous, composed of different halogens inside and out, or layered. Different silver halides can be formed by epitaxial bonding, for example, bonding with compounds other than silver halides such as silver thiocyanate and lead oxide. Furthermore, mixtures of particles with various crystal forms can be used.

[0232] The emulsion described above can be any of the following types: surface latent image type, internal latent image type, or type with latent images on both the surface and inside the particles, but it must be a negative emulsion. Among the internal latent image type, it can be a core / shell type internal latent image emulsion as described in Japanese Patent Application Publication No. 63-264740, the preparation method of which is described in Japanese Patent Application Publication No. 59-133542. The shell thickness of this emulsion varies depending on the development process, etc., and is preferably 3 nm to 40 nm, particularly preferably 5 nm to 20 nm.

[0233] Silver halide emulsions typically use silver halide emulsions that have undergone physical curing, chemical curing, and spectral sensitization. The additives used in this process are described in RD No. 17643, RD No. 18716, and RD No. 307105, the relevant portions of which are summarized in the table below.

[0234] In the photographic silver halide material of the present invention, two or more emulsions with at least one different characteristic in terms of particle size, particle size distribution, halogen composition, particle shape, and photosensitivity of the photosensitive silver halide emulsion can be mixed and used in the same layer. Preferably, silver halide particles that cause surface fogging as described in U.S. Patent No. 4,082,553, silver halide particles that cause internal fogging as described in U.S. Patent No. 4,626,498, and Japanese Patent Application Publication No. 59-214852, colloidal silver are used in the photosensitive silver halide emulsion layer and / or substantially non-photosensitive hydrophilic colloidal layer. Silver halide particles that cause internal or surface fogging refer to silver halide particles that can be uniformly (non-imagingly) developed regardless of the unexposed or exposed portions of the photosensitive material. Their preparation method is described in U.S. Patent No. 4,626,498 and Japanese Patent Application Publication No. 59-214852. The halogen composition of the silver halide in the internal core of the core / shell type silver halide particles that form internal fogging can be different. Any one of silver chloride, silver chlorobromide, silver iodide bromide, or silver chloroiodide bromide can be used as the silver halide for internal or surface fogging. The average particle size of these fogged silver halide particles is preferably 0.01 μm to 0.75 μm, and particularly preferably 0.05 μm to 0.6 μm. Furthermore, the particle shape can be regular particles or a polydisperse emulsion, but monodispersity is preferred (at least 95% of the mass or number of silver halide particles has a particle size within ±40% of the average particle size).

[0235] In this invention, non-photosensitive particulate silver halide is preferably used. Non-photosensitive particulate silver halide refers to silver halide particles that are not photosensitive during imaging exposure for obtaining pigment images and are substantially not developed during their development process; preferably, they are not pre-coated. The particulate silver halide contains 0 to 100 mol% silver bromide and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% silver iodide. The average particle size (average value of the equivalent circle diameter of the projected area) of the particulate silver halide is preferably 0.01 μm to 0.5 μm, more preferably 0.02 μm to 0.2 μm.

[0236] Particulate silver halide can be prepared using the same methods as conventional photosensitive silver halide. The surface of the silver halide particles does not require optical or spectral sensitization. However, it is preferable to pre-add a known stabilizer, such as a triazole, azidoinden, benzothiazolium, thiol, or zinc compound, before adding it to the coating solution. Colloidal silver can be contained within the layer containing these particulate silver halide particles.

[0237] The preferred silver coating amount of the silver halide photographic photosensitive material involved in this invention is 6.0 g / m². 2 The following is more preferably 4.5 g / m 2 the following.

[0238] Photographic additives that can be used in this invention are also described in RD, and the descriptions related to the table below are shown.

[0239] [Table 1]

[0240] Various pigments can be used to form colorants in the silver halide photographic materials involved in this invention, but the following colorants are particularly preferred.

[0241] Yellow coloring agents: coloring agents represented by formulas (I) and (II) in EP502,424A; coloring agents represented by formulas (1) and (2) in EP513,496A (especially Y-28 on page 18); coloring agents represented by formula (I) of claim 1 in EP568,037A; coloring agents represented by general formula (I) in lines 45-55 of column 1 of the specification of U.S. Patent No. 5,066,576; coloring agents represented by general formula (I) in paragraph 0008 of Japanese Patent Application Publication No. 4-274425. Coloring agents shown; coloring agents described in claim 1 on page 40 of EP498,381A1 (especially D-35 on page 18); coloring agents represented by formula (Y) on page 4 of EP447,969A1 (especially Y-1 (page 17), Y-54 (page 41)); coloring agents represented by formulas (II) to (IV) on lines 36 to 58 of column 7 of the specification of U.S. Patent No. 4,476,219 (especially II-17, 19 (column 17), II-24 (column 19)).

[0242] Magenta coloring agent: Japanese Patent Application Publication No. 3-39737 (L-57 (page 11, bottom right), L-68 (page 12, bottom right), L-77 (page 13, bottom right); EP456,257 A-4-63 (page 134), A-4-73, -75 (page 139); EP486,965 M-4, -6 (page 26), M-7 (page 27); EP571,959A M-45 (page 19); Japanese Patent Application Publication No. 5-204106 (M-1) (page 6); Japanese Patent Application Publication No. 4-362631, paragraph 0237, M-22.

[0243] Cyan colorant: CX-1, 3, 4, 5, 11, 12, 14, 15 (pages 14-16) of Japanese Patent Application Publication No. 4-204843; C-7, 10 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42-43) of Japanese Patent Application Publication No. 4-43345; colorant represented by general formula (Ia) or (Ib) of claim 1 of Japanese Patent Application Publication No. 6-67385.

[0244] Polymer colorants: P-1 and P-5 of Japanese Patent Application Publication No. 2-44345 (11 pages).

[0245] As a colorant with suitable diffusivity, the colorants described in U.S. Patent No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,873B, and German Patent No. 3,234,533 are preferred.

[0246] The preferred colorants for correcting unwanted absorption of chromogenic pigments are yellow and cyan colorants represented by formulas (CI), (CII), (CIII), and (CIV) as described on page 5 of European Patent Application Publication No. 456,257A1 (especially YC-86 on page 84), yellow and magenta colorants ExM-7 (page 202), EX-1 (page 249), and EX-7 (page 251) as described in European Patent Application Publication No. 456,257A1, magenta and cyan colorants CC-9 (column 8) and CC-13 (column 10) as described in U.S. Patent No. 4,833,069, magenta and cyan colorants (2) (column 8) as described in U.S. Patent No. 4,837,136, and colorless masking colorants represented by formula (A) as described in claim 1 of International Publication No. 92 / 11575 (especially the illustrative compounds on pages 36-45).

[0247] As colorants that release photographically useful groups, the following colorants can be cited: Developer inhibitor releasing compounds: compounds represented by formulas (I), (II), (III), and (IV) described on page 11 of European Patent Application Publication No. 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 (page 36), T-131 (page 45), T-144 (page 51), and T-158 (page 58)); compounds represented by formula (I) described on page 7 of European Patent Application Publication No. 436,938A2 (especially D-49 (page 51)); European... Compounds represented by formula (1) in the specification of Patent Application Publication No. 568,037A (especially (23) (page 11)), compounds represented by formulas (I), (II), and (III) described on pages 5-6 of the specification of European Patent Application Publication No. 440,195A2 (especially I-(1) on page 29); bleaching accelerator release compounds: compounds represented by formulas (I) and (I') on page 5 of the specification of European Patent Application Publication No. 310,125A2 (especially (60) and (61) on page 61) and Japanese Patent Application Publication No. 6-59411 The compound represented by formula (I) of claim 1 of the specification (especially (7) (page 7); ligand-releasing compounds: the compound represented by LIG-X of claim 1 as described in the specification of U.S. Patent No. 4,555,478 (especially the compounds in columns 21-41 of column 12); colorless pigment-releasing compounds: compounds 1-6 in columns 3-8 of the specification of U.S. Patent No. 4,749,641; fluorescent pigment-releasing compounds: the compound represented by COUP-DYE of claim 1 as described in the specification of U.S. Patent No. 4,774,181 (especially Compounds 1-11 in columns 7-10); developer-enhancing or anti-fogging agent releasing compounds: compounds represented by formulas (1), (2), and (3) in column 3 of U.S. Patent No. 4,656,123 (especially (I-22) in column 25) and ExZK-2 on page 75, lines 36-38 of EP450,637A2; compounds that release groups that begin to become pigments after dissociation: compounds represented by formula (I) in claim 1 of U.S. Patent No. 4,857,447 (especially Y-1-Y-19 in columns 25-36).

[0248] As additives other than colorants, the following additives are preferred: Dispersion media for oil-soluble organic compounds: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (pp. 140-144) of Japanese Patent Application Publication No. 62-215272; Latex for impregnation of oil-soluble organic compounds: Latex as described in the specification of US Patent No. 4,199,363; Oxidation scavenger of developing agent: Compounds represented by formula (I) in lines 54-62 of column 2 of the specification of US Patent No. 4,978,606 (especially I-, (1), (2), (6), (12) (columns 4-5), and compounds represented by formula (I-) in lines 54-62 of column 2 of the specification of US Patent No. 4,923,787. Formulas in line 0 (especially compound 1 (column 3)); Antifouling agents: Formulas (I) to (III) in lines 30 to 33 of page 4 of European Patent Application Publication No. 298321A, especially I-47, 72, III-1, 27 (pages 24 to 48); Antifading agents: A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 in European Patent Application Publication No. 298321A (pages 69 to 118), II-1 to III-23 in columns 25 to 38 of U.S. Patent No. 5,122,444, especially III-10, European Patent Application Publication No. 298321A ... The following are examples of materials used in patent application publication No. 471347A: pages 8-12, sections I-1-III-4, especially II-2; and columns 32-40, sections A-1-48, especially A-39 and 42; materials for reducing the amount of color-enhancing agents or anti-mixing agents: pages 5-24, sections I-1-II-15, especially I-46; formaldehyde scavengers: pages 24-29, sections SCV-1-28, especially SCV-8; film-hardening agents: page 17, section H-1 of Japanese Patent Application Publication No. 1-214845. 4, 6, 8, 14, compounds represented by formulas (VII) to (XII) in columns 13 to 23 of U.S. Patent No. 4,618,573 (H-1 to 54), compounds represented by formula (6) in the lower right corner of page 8 of Japanese Patent Application Publication No. 2-214852 (H-1 to 76), especially H-14, compounds described in claim 1 of U.S. Patent No. 3,325,287; precursors of imaging inhibitors: P-24, 37, 39 of Japanese Patent Application Publication No. 62-168139 (pages 6 to 7); compounds described in claim 1 of U.S. Patent No. 5,019,492, especially 28 and 29 in column 7;Preservatives and mildew inhibitors: I-1 to III-43, especially II-1, 9, 10, 18, and III-25, in columns 3 to 15 of the specification of U.S. Patent No. 4,923,790; Stabilizers and anti-fogging agents: I-1 to (14), especially I-1, 60, (2), and (13), in columns 6 to 16 of the specification of U.S. Patent No. 4,952,483; and compounds 1 to 65, especially 36, in columns 25 to 32 of the specification of U.S. Patent No. 4,952,483; Chemical sensitizers: triphenylphosphine selenide and compounds disclosed in Japanese Patent Application Publication No. 5-40324. Article 50; Dyes: Japanese Patent Application Publication No. 3-156450, pages 15-18, a-1-b-20, especially a-1, 12, 18, 27, 35, 36, b-5; pages 27-29, V-1-23, especially V-1; European Patent Application Publication No. 445627A, pages 33-55, FI-1-F-II-43, especially FI-11, F-II-8; European Patent Application Publication No. 457153A, pages 17-28, III-1-36, especially III-1, 3; Microcrystalline dispersions of Dye-1 to 124 on pages 8 to 26 of International Patent Publication No. 88 / 04794; compounds 1 to 22 on pages 6 to 11 of specification No. EP319999A, especially compound 1; compounds D-1 to 87 represented by formulas (1) to (3) in European Patent Application Publication No. 519306A (pages 3 to 28); compounds 1 to 22 represented by formula (I) in specification No. 4,268,622 (columns 3 to 10); compounds (1) represented by formula (I) in specification No. 4,923,788. (31) (Columns 2-9); UV absorbers: compounds (18b) to (18r) and 101 to 427 (pages 6-9) represented by formula (1) in Japanese Patent Application Publication No. 46-3335, compounds (3) to (66) represented by formula (I) (pages 10-44) and compounds HBT-1 to 10 represented by formula (III) (page 14) in European Patent Application Publication No. 520938A, and compounds (1) to (31) represented by formula (1) (Columns 2-9) in European Patent Application Publication No. 521823A.

[0249] This invention is applicable to various color photosensitive materials, including black and white photographic paper, black and white negative film, X-ray film, general-purpose or cinematic color negative film, color reversal film for slides or television, color photographic paper, color positive film, and color reversal photographic paper. Furthermore, it is suitable for use with lens-mounted film units as described in Japanese Patent Publication No. 2-32615 and Japanese Utility Publication No. 3-39784.

[0250] Suitable supports that can be used in this invention are described, for example, on page 28 of RD. No. 17643, from the right column of page 647 to the left column of page 648 of RD. No. 18716, and on page 879 of RD. No. 307105.

[0251] In the silver halide photographic photosensitive material of the present invention, the total thickness of the total hydrophilic colloidal layer on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. Furthermore, the film swelling rate T... 1 / 2 Preferably, it is 30 seconds or less, more preferably 20 seconds or less. 1 / 2 Defined as the time until the film thickness reaches half of 90% of the maximum swelling film thickness achieved when treated with colorimetric developer at 30°C for 3 minutes and 15 seconds. Film thickness refers to the film thickness measured (after 2 days) under conditioned conditions of 25°C and 55% relative humidity. T 1 / 2 It can be measured using the dilatometer (sweller) of the type described by A. Green et al. in Photogr. Sci. Eng., Vol. 19, 2, pp. 124-129. T 1 / 2 The swelling ratio can be adjusted by adding a film-hardening agent to the gelatin used as a binder or by changing the post-coating time conditions. Furthermore, the swelling ratio is preferably 150% to 400%. The swelling ratio refers to the maximum swollen film thickness that can be achieved under the above conditions.

[0252] Formula: (maximum swelling film thickness - film thickness) / film thickness

[0253] To calculate.

[0254] The silver halide photographic material of this invention preferably has a hydrophilic colloidal layer (referred to as a back layer) with a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, light-filtering dye, ultraviolet absorber, antistatic agent, film-hardening agent, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of this back layer is preferably 150% to 500%.

[0255] The silver halide photographic material involved in this invention can be developed using the conventional methods described in pages 28-29 of RD. No. 17643, pages 651 (left and right columns) of RD. No. 18716, and pages 880-881 of RD. No. 307105.

[0256] Furthermore, in this invention, an antistatic agent is preferably used.

[0257] Examples of such antistatic agents include polymers containing carboxylic acids and their salts, sulfonates, cationic polymers, ionic surfactant compounds, and conductive polymers with π-electron conjugated systems. Preferred antistatic agents are at least one material selected from ZnO, TiO2, SnO2, Al2O3, In2O3, SiO2, MgO, BaO, MoO3, and V2O5 with a volume resistivity of 10 Ω·cm. 7 Ω·cm or less, more preferably 10 5 The silver halide photosensitive material contains crystalline metal oxides or composite oxides of these (Sb, P, B, In, S, Si, C, etc.) with a particle size of 0.001 μm to 1.0 μm or less (Ω·cm), and further comprises sol-like metal oxides or composite oxides of these. The preferred content in the silver halide photosensitive material is 5 mg / m³. 2 ~500mg / m 2 10 mg / m² is particularly preferred. 2 ~350mg / m 2 The ratio of the conductive crystalline oxide or its composite oxide to the binder is preferably 1 / 300 to 100 / 1, more preferably 1 / 100 to 100 / 5. Examples of conductive polymers with π-electron conjugation systems include polythiophene compounds, polypyrrole compounds, and polyfuran compounds. It is preferable to use a latex-like aqueous dispersion containing a polythiophene compound and a polymeric polyanionic compound. The detailed structure of the compound, the composition of the dispersion, and the preferred manner of using the dispersant can be described using the methods described in Japanese Patent Application Publication No. 2003-330145, Japanese Patent No. 4244541, Japanese Patent Application Publication No. 2016-120650, and Japanese Patent Application Publication No. Hei 8-211615.

[0258] In the silver halide photographic material according to the present invention, slip properties are preferred. The lubricant-containing layer is preferably used on both the photosensitive surface and the back surface. Preferred slip properties are a coefficient of kinetic friction of 0.01 or higher and 0.25 or lower. This measurement represents the value relative to a 5mm diameter stainless steel ball being transported at 60cm / min (25°C, 60%RH). In this evaluation, even if the photosensitive surface is replaced with the mating material, the value remains approximately the same.

[0259] Examples of lubricants that can be used in this invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, and esters of higher fatty acids and higher alcohols. Among the polyorganosiloxanes, polydimethylsiloxane, polydiethylsiloxane, polystyrene-methylsiloxane, and polymethylphenylsiloxane can be used. As an additive layer, the outermost layer or backing layer of the emulsion layer is preferred. Polydimethylsiloxane or esters having long-chain alkyl groups are particularly preferred.

[0260] The silver halide photographic material of the present invention preferably contains a matting agent. The matting agent can be either the emulsion side or the back side, but is particularly preferably added to the outermost layer of the emulsion side. The matting agent can be soluble in the processing solution or insoluble in the processing solution, preferably both. For example, polymethyl methacrylate, poly(methyl methacrylate / methacrylic acid = 9 / 1 or 5 / 5 (molar ratio)), polystyrene particles, etc., are preferred. The particle size is preferably 0.8 μm to 10 μm, and the particle size distribution is also preferably narrow, preferably containing more than 90% of the total number of particles between 0.9 and 1.1 times the average particle size. Furthermore, to improve matting properties, it is also preferable to simultaneously add particles smaller than 0.8 μm, such as polymethyl methacrylate (0.2 μm), poly(methyl methacrylate / methacrylic acid = 9 / 1 (molar ratio), 0.3 μm), polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).

[0261] The silver halide photographic material involved in this invention can contain other known additives in each layer.

[0262] Furthermore, even if the silver halide photographic material of the present invention does not have photosensitive properties to X-ray irradiation, the structure and components of the silver halide photographic material with photosensitive properties to X-ray irradiation described later can be used as needed.

[0263] Furthermore, the following describes silver halide photographic materials that are sensitive to X-ray irradiation.

[0264] As a photographic photosensitive material of silver halide, silver halide photographic photosensitive materials with photosensitivity to X-ray irradiation can be preferred.

[0265] Silver halide emulsion

[0266] First, the silver halide emulsion used in this invention will be described.

[0267] 1) Halogen composition

[0268] Photosensitive silver halide particles can be silver chloride, silver chlorobromide, silver bromide, silver iodide bromide, or silver iodide-chlorobromide. However, from the viewpoint of rapid processing as described above, the iodine content contained in the photosensitive silver halide particles is preferably 0 mol% or more and 0.45 mol% or less on average. More preferably, it is 0.05 mol% or more and 0.40 mol% or less on average, and even more preferably 0.10 mol% or more and 0.30 mol% or less. Here, "average" of the iodine content contained in the photosensitive silver halide particles refers to the average iodine content calculated based on the halogen composition of each photosensitive silver halide particle. The distribution of the halogen composition within the photosensitive silver halide particles can be uniform, the halogen composition can vary stepwise, or it can vary continuously. Furthermore, photosensitive silver halide particles with a core / shell structure can also be used as photosensitive silver halide particles.

[0269] 2) Particle shape

[0270] As photosensitive silver halide particles, preferred examples include so-called halogen conversion type particles as described in British Patent No. 635,841 and US Patent No. 3,622,318. Halogen conversion is typically performed by adding an aqueous halogen solution with a solubility product with silver that is smaller than the halogen composition on the particle surface before conversion. For example, potassium bromide and / or potassium iodide aqueous solutions are added to silver chloride or silver chlorobromide plate particles, and potassium iodide aqueous solution is added to silver bromide or silver iodide bromide plate particles for conversion. The concentration of these added aqueous solutions is preferably low, preferably 30% or less, more preferably 10% or less. Furthermore, the conversion halogen solution is preferably added at a rate of 1 mol% or less per minute for every 1 mole of silver halide before conversion. Moreover, during halogen conversion, some or all of the saturating agent and / or silver halide adsorbent may be present, and silver halide particles such as silver bromide, silver iodide bromide, or silver iodide may be added instead of the aqueous conversion halogen solution. These particles are preferably 0.2 μm or less, more preferably 0.1 μm or less, and especially preferably 0.05 μm or less. The halogen conversion method is not limited to the methods described above and can be appropriately combined depending on the purpose.

[0271] 3) Particle size

[0272] Methods for forming photosensitive silver halide particles are well known in the art, for example, they can be prepared by using methods described in Japanese Patent Application Publication No. 2-68539, U.S. Patent No. 3,700,458, and Research Disclosure No. 17029 of June 1978.

[0273] 4) Chemical sensitization method

[0274] As a chemical sensitization method, the methods described in Japanese Patent Application Publication No. 2-68539, page 10, upper right column, line 13 to lower left column, line 16, Japanese Patent Application Publication No. 5-313282, and Japanese Patent Application Publication No. 6-110144 can be used.

[0275] As a method for chemical sensitization of silver halide emulsions, specifically, known methods such as sulfur sensitization, selenium sensitization, reduction sensitization, and gold sensitization can be used in the presence of silver halide adsorbents, and can be used alone or in combination.

[0276] Among precious metal sensitization methods, gold sensitization is a representative method, using gold compounds, primarily gold complexes. It may also contain precious metals other than gold, such as platinum, palladium, and iridium complexes. Specific examples are described in U.S. Patent No. 2,448,060, British Patent No. 618,061, and others.

[0277] In addition to the sulfur compounds contained in gelatin, various sulfur compounds, such as thiosulfates, thioureas, thiazoles, and rhodanines, can be used as sulfur sensitizers. Specific examples include compounds described in U.S. Patent Nos. 1,574,944, 2,278,947, 2,410,689, 2,728,668, 5,501,313, and 3,656,955. Furthermore, selenium sensitizers are described in Japanese Patent Application Publication No. 6-110144.

[0278] The combined use of sulfur sensitizers, selenium sensitizers, and gold sensitizers based on thiosulfates is useful. Stannous salts, amines, formamidinium disulfide acids, silane compounds, etc., can be used as reducing sensitizers.

[0279] 5) Anti-fogging agents and stabilizers

[0280] As an anti-fogging agent and stabilizer, the compounds described in Japanese Patent Application Publication No. 2-68539, page 10, bottom left column, line 17 to page 11, top left column, line 7, and page 3, bottom left column, line 2 to page 4, bottom left column, can be used.

[0281] Specifically, compounds known to be added as antifogging agents or stabilizers include azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); thiolated compounds (e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.); thionone compounds such as oxazolinethione; azaindenes (e.g., triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.); benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamides, etc.

[0282] In particular, nitrones and their derivatives described in Japanese Patent Application Publication No. 60-76743 and No. 60-87322, mercapto compounds described in Japanese Patent Application Publication No. 60-80839, heterocyclic compounds and complex salts of heterocyclic compounds and acids (e.g., 1-phenyl-5-mercaptotetrazoles) described in Japanese Patent Application Publication No. 57-164735 are preferred.

[0283] Furthermore, purine compounds, nucleic acid compounds, or polymeric compounds as described in Japanese Patent Publication No. 61-36213 and Japanese Patent Application Publication No. 59-90844 can also be used. Among these, azaindene compounds, purine compounds, and nucleic acid compounds are particularly preferred. The amount of these compounds added relative to 1 mole of silver halide is preferably 0.5 mmol to 5.0 mmol, more preferably 0.5 mmol to 3.0 mmol.

[0284] 6) Color Improver

[0285] As color tone improvers, examples include those described in Japanese Patent Application Publication No. 62-276539, page 2, bottom left column, line 7 to page 10, bottom left column, line 20, and Japanese Patent Application Publication No. 3-94249, page 6, bottom left column, line 15 to page 11, top right column, line 19.

[0286] Specifically, the coverage of the silver halide photographic emulsion layer is set to 60 or higher, and the silver halide photographic emulsion layer and / or other layers contain dyes with extremely high absorption wavelengths between 520 nm and 560 nm and dyes with extremely high absorption wavelengths between 570 nm and 700 nm, in such a way that the increase in optical concentration of the unexposed portion after development treatment based on the optical concentration containing the dye is less than 0.03.

[0287] Examples of emulsions that achieve a coverage of 60 or higher for silver halide photographic emulsions include flat emulsions and particulate emulsions. In particular, the effect of color tone improvement is significant when the silver halide photographic emulsion is formed from flat silver halide particles with a particle thickness of less than 0.4 μm, or when a mixed emulsion is used that combines a high-iodine surface-sensitive emulsion with an emulsion formed from particles with internal gray-fog-like inclusions.

[0288] As dyes that can be used for tone improvement, examples include the combination of dyes with a maximum absorption wavelength preferably between 520 nm and 560 nm, more preferably between 530 nm and 555 nm, and dyes with a maximum absorption wavelength preferably between 570 nm and 700 nm, more preferably between 580 nm and 650 nm. The maximum absorption wavelength refers to the maximum absorption wavelength in which the dye is present in the photosensitive material.

[0289] As dyes, dyes with a specified maximum wavelength are selected from anthraquinone dyes, azo dyes, azomethyl dyes, indigoaniline dyes, oxacyanine dyes, carbocyanine dyes, styrene dyes, triphenylmethane dyes, etc. When considering the effects on the stability of the developing process, light fastness, and photographic properties such as desensitization, fogging, and staining, preferred dyes from anthraquinone dyes, azo dyes, azomethyl dyes, and indigoaniline dyes are used. Preferred compounds are described in Japanese Patent Application Publication No. 62-276539, page 3, top left column, line 5 to page 9, top left column, line 9.

[0290] This dye can be dispersed in emulsion layers or other hydrophilic colloidal layers (intermediate layers, protective layers, anti-halo layers, filter layers, etc.) by various known methods, specifically as described in Japanese Patent Application Publication No. 62-276539, page 9, top left column, line 14 to page 10, bottom left column, line 20.

[0291] 7) Spectral Enhancement of Infected Materials

[0292] As a spectral enrichment material, the spectral enrichment material described in Japanese Patent Application Publication No. 2-68539, page 4, bottom right column, line 4 to page 8, bottom right column, can be cited as an example.

[0293] Specifically, it can use anthocyanin, partial anthocyanin, complex anthocyanin, complex partial anthocyanin, full polyene pigment, styryl pigment, hemicyanin, oxocyanine pigment, hemicyanine pigment, etc.

[0294] Infectious materials are described, for example, in U.S. Patent No. 3,522,052, U.S. Patent No. 3,617,197, U.S. Patent No. 3,713,828, U.S. Patent No. 3,615,643, U.S. Patent No. 3,615,632, U.S. Patent No. 3,617,293, U.S. Patent No. 3,628,964, U.S. Patent No. 3,703,377, U.S. Patent No. 3,666,480, U.S. Patent No. 3,667,960, U.S. Patent No. 3,679,428, U.S. Patent No. 3,672,897, U.S. Patent No. 3,769,026, U.S. Patent No. 3,556,800, U.S. Patent No. 3,615,613, and other U.S. patents. Patent No. 3,613,638, U.S. Patent No. 3,615,635, U.S. Patent No. 3,705,809, U.S. Patent No. 3,632,349, U.S. Patent No. 3,677,765, U.S. Patent No. 3,770,449, U.S. Patent No. 3,770,440, U.S. Patent No. 3,769,025, U.S. Patent No. 3,745,014, U.S. Patent No. 3,713,826, U.S. Patent No. 3,567,458, U.S. Patent No. 3,625,698, U.S. Patent No. 2,526,632, U.S. Patent No. 2,503,776, Japanese Patent Application Publication No. 48-76525, Belgian Patent No. 691807, etc. The amount of the infectious agent added relative to each mole of silver halide is preferably 0.5 mmol or more and less than 4 mmol, more preferably 0.5 mmol or more and less than 1.5 mmol.

[0295] As a specific example of materials that increase infection, we can cite II-1 to II-47 as recorded on pages 5 to 8 of Japanese Patent Application Publication No. 2-68539.

[0296] 8) Antistatic agent

[0297] In this invention, the surfactant described in Japanese Patent Application Publication No. 2-68539, page 11, top left column, line 14 to page 12, top left column, line 9, can be used as a coating aid, antistatic agent, or charge modifier.

[0298] Furthermore, the ionic compounds involved in this invention can be used as coating aids, antistatic agents, or charge modifiers.

[0299] Specific examples of surfactants used for this purpose include nonionic surfactants such as saponins (steroidal), epoxide derivatives (e.g., polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, silicone polyethylene oxide compounds), and alkyl esters of sugars; anionic surfactants such as alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, sulfosuccinates, and sulfoalkylpolyoxyethylene alkylphenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; and cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts, and imidazoline salts.

[0300] Among them, the following are particularly preferred: anionic saponins, sodium dodecylbenzenesulfonate, di-2-ethylhexyl α-sulfosuccinate Na salt, p-octylphenoxyethoxyethanesulfonate Na salt, dodecyl sulfate Na salt, triisopropylnaphthalenesulfonate Na salt, N-methyl-oleoyl taurate Na salt, etc.; cationic saponins, such as dodecyltrimethylammonium chloride, N-oleoyl-N',N',N'-trimethylammonium diaminopropane bromide, dodecylpyridinium chloride, etc.; betaines, such as N-dodecyl-N,N-dimethylcarboxybetaine, N-oleenyl-N,N-dimethylsulfobutyl betaine, etc.; poly(average degree of polymerization n-10)oxyethylene hexadecyl ether, poly(n=25)oxyethylene p-nonylphenol ether, bis(1-poly(n=15)oxyethylene-oxy-2,4-di-tert-butylphenyl) ethane, etc.

[0301] Furthermore, as an antistatic agent, nonionic surfactants, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides doped with antimony as described in Japanese Patent Application Publication Nos. 60-80848, 61-112144, 62-172343, and 62-173459 are preferred.

[0302] 9) Matting agents, lubricants and plasticizers

[0303] As a matting agent, lubricant and plasticizer, examples can be found in Japanese Patent Application Publication No. 2-68539, page 12, top left column, line 10 to top right column, and page 14, bottom left column, line 10 to bottom right column, line 1.

[0304] Specifically, as a matting agent, homopolymers of polymethyl methacrylate or copolymers of methyl methacrylate and methacrylic acid as described in U.S. Patent Nos. 2,992,101, 2,701,245, 4,142,894, and 4,396,706, as well as organic compounds such as starch, and inorganic compounds such as silica, titanium dioxide, sulfuric acid, and barium strontium, can be used. The particle size is preferably 1.0 μm to 10 μm, and particularly preferably 2 μm to 5 μm.

[0305] In the surface layer of the silver halide photographic photosensitive material involved in this invention, in addition to silicone compounds described in U.S. Patent No. 3,489,576 and U.S. Patent No. 4,047,958, and colloidal silica described in Japanese Patent Publication No. 56-23139, paraffin wax, higher fatty acid esters, starch derivatives, etc., can also be used as lubricants.

[0306] In the hydrophilic colloidal layer of the silver halide photographic material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, and glycerol can be used as plasticizers. Furthermore, in the emulsion layer of the silver halide photographic material of the present invention, polymers or emulsions can be contained as plasticizers to improve pressure characteristics.

[0307] For example, British Patent No. 738618 discloses a method using heterocyclic compounds, British Patent No. 738637 discloses a method using alkyl phthalates, British Patent No. 738639 discloses a method using alkyl esters, US Patent No. 2,960,404 discloses a method using polyols, US Patent No. 3,121,060 discloses a method using carboxyalkyl cellulose, Japanese Patent Application Publication No. 49-5017 discloses a method using paraffin and carboxylates, and Japanese Patent Application Publication No. 53-28086 discloses a method using alkyl acrylates and organic acids, etc., and these methods can also be used in the present invention.

[0308] 10) Hydrophilic colloids

[0309] Gelatin is advantageously used as a binder or protective colloid that can be used in the emulsion layer, intermediate layer and surface protective layer of the silver halide photographic material involved in this invention, but other hydrophilic colloids can also be used.

[0310] As examples of hydrophilic colloids, the hydrophilic colloids described in Japanese Patent Application Publication No. 2-68539, page 12, upper right column, line 11 to lower left column, line 16, can be cited.

[0311] For example, it can use gelatin derivatives, graft polymers of gelatin with other high molecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives; and homopolymers or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazolium, and polyvinylpyrazole, as well as many other synthetic hydrophilic polymers.

[0312] In addition to lime treatment, gelatin can also be treated with acid or enzymes, and gelatin hydrolysates or enzyme decomposition products can also be used.

[0313] Preferably, dextran or polyacrylamide with an average molecular weight of less than 100,000 is used in combination with gelatin. The methods described in Japanese Patent Application Publication Nos. 63-68887 and 63-149641 can also be used in this invention.

[0314] 11) Hardening agent

[0315] Photographic emulsions and non-photosensitive hydrophilic colloids may contain inorganic or organic hardening agents.

[0316] As a hardening agent, the hardening agent described in Japanese Patent Application Publication No. 2-68539, page 12, bottom left column, line 17 to page 13, top right column, line 6, can be cited.

[0317] Specifically, for example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-hydroxymethyl compounds (dihydroxymethylurea, hydroxymethyl dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-(β-(vinylsulfonyl)propionamide), etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), viscous halogen acids (viscous chloric acid, viscous phenoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazine gelatin, etc., can be used alone or in combination. Among them, the active vinyl compounds described in Japanese Patent Application Publication No. 53-41221, Japanese Patent Application Publication No. 53-57257, Japanese Patent Application Publication No. 59-162546, and Japanese Patent Application Publication No. 60-80846, and the active halides described in US Patent No. 3,325,287 are preferred.

[0318] As a film-hardening agent, it can also effectively utilize polymeric film-hardening agents.

[0319] Examples of polymeric film-forming agents include, for example, dialdehyde starch, polyacrylaldehyde, acrolein copolymers and other polymers containing aldehyde groups as described in U.S. Patent No. 3,396,029, epoxy-containing polymers as described in U.S. Patent No. 3,623,878, dichlorotriazine-containing polymers as described in U.S. Patent No. 3,362,827, Research Disclosure No. 17333 (1978), polymers containing active ester groups as described in Japanese Patent Application Publication No. 56-66841, Japanese Patent Application Publication No. 56-142524, U.S. Patent No. 4,161,407, Japanese Patent Application Publication No. 54-65033, and Research... Polymers having active vinyl groups or groups that serve as precursors, as described in Disclosure magazine No. 16725 (1978), are preferred. Among them, polymers having active vinyl groups or groups that serve as precursors are particularly preferred, such as those described in Japanese Patent Application Publication No. 56-142524, which are polymers bonded to the polymer backbone by long-spaced active vinyl groups or groups that serve as precursors.

[0320] The hydrophilic colloidal layer in the silver halide photographic material involved in this invention is preferably hardened by these hardening agents so that the swelling rate in water is less than 300%, and more particularly less than 230%.

[0321] 12) Support

[0322] As a support, the support described in the upper right column, lines 7 to 20, on page 13 of Japanese Patent Application Publication No. 2-68539 can be cited. Specifically, polyethylene terephthalate film or cellulose triacetate film are preferred as supports.

[0323] To improve the adhesion to the hydrophilic colloidal layer, the support is preferably subjected to corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment on its surface. Alternatively, a lower coating layer formed of styrene-butadiene latex, vinylidene chloride latex, etc., can be provided, and a gelatin layer can be further provided on top of it.

[0324] Furthermore, an undercoat can be applied using an organic solvent containing polyethylene swelling agent and gelatin. These undercoats can also have their adhesion to the hydrophilic colloidal layer further improved through surface treatment.

[0325] 13) Cross-exposure suppression method

[0326] It is a well-known fact in the art that cross-exposure light significantly reduces sharpness. As a method to reduce the cross-exposure light of photographic photosensitive materials to 12% or less, U.S. Patent No. 4,130,429, Japanese Patent Application Publication No. 61-116354, and other methods disclose the use of staining materials or dyes to absorb light with a wavelength that matches the emission wavelength of an X-ray fluorescent screen.

[0327] Furthermore, U.S. Patent No. 4,800,150 discloses a technique that presents dye in the form of a microcrystalline dispersion between a support and an emulsion layer, thereby reducing cross-exposure light to 10% or less. Japanese Patent Application Publication No. 63-305345 discloses a technique for fixing anionic dyes to a specific layer using a cationic polymer latex. Furthermore, Japanese Patent Application Publication No. 1-166031 discloses a technique for using a dye-fixing layer as a base layer for the support. In the photosensitive material according to the present invention, any of these methods can be used, but the dye-based coloring layer is preferably a base layer, and the dye is preferably fixed by the method described in Japanese Patent Application Publication No. 1-166031, and particularly preferably the dye is fixed to the base layer in the form of a microcrystalline dispersion as described in U.S. Patent No. 4,803,150. In the present invention, these methods can be appropriately combined.

[0328] As preferred dyes, examples include those listed in the lower left column of page 4 to the upper right column of page 9 of Japanese Patent Application Publication No. 2-264944.

[0329] Furthermore, as a mordant layer, the mordant layer described in the lower right column of page 9 to the upper right column of page 14 of Japanese Patent Application Publication No. 2-264944 can be used.

[0330] 14) Polyhydroxybenzenes

[0331] Examples of polyhydroxybenzenes include those described in the upper left column of page 11 to the lower left column of page 12 of Japanese Patent Application Publication No. 3-39948 and in the specification of European Patent Application Publication No. 452772A.

[0332] Specifically, examples include the compound of general formula (III) recorded in the upper left column of page 11 of Japanese Patent Application Publication No. 3-39948, and the specific compounds are compounds (III)-1 to (III)-25 recorded in the lower left column of page 11 to the lower left column of page 12 of Japanese Patent Application Publication No. 3-39948.

[0333] As for the amount of these polyhydroxybenzene compounds added, as long as each mole of silver halide is less than 5 × 10⁻⁶. -1 Moles are acceptable, but preferably 5 × 10⁻⁶ moles of silver halide per mole are preferred. -3 mole ~ 1×10 -1 The amount of mole added.

[0334] The photographic photosensitive material of silver halide involved in this invention is composed of a silver halide emulsion layer (photosensitive layer) containing photosensitive silver halide particles on a support and at least one non-photosensitive hydrophilic colloidal layer, such as an intermediate layer, a surface protective layer, a back layer, a back protective layer, an anti-halo layer, and a filter layer. However, there are no particular limitations on other emulsion sensitization methods or various additives used. For example, the emulsion sensitization methods or various additives described in Japanese Patent Application Publication No. 2-68539 are preferred.

[0335] 15) Surface protective layer and back protective layer

[0336] The silver halide photographic photosensitive material of this invention preferably has a surface protective layer and a back protective layer, wherein the surface protective layer and the back protective layer contain various chemicals, with hydrophilic colloids such as gelatin as binders. When the main component of this layer is gelatin, preservatives are required. Furthermore, it is preferable to include, as needed, matting agents, lubricants, plasticizers, antistatic agents, surfactants, film-hardening agents, thickeners, dyes, conductive substances, etc.

[0337] 16) Development Processing Method

[0338] The developing method for the silver halide photographic photosensitive material according to the present invention can employ the methods described in Japanese Patent Application Publication No. 2-103037 (page 16, top right column, line 7 to page 19, bottom left column, line 15), Japanese Patent Application Publication No. 2-115837 (page 3, bottom right column, line 5 to page 6, top right column, line 10), and Japanese Patent Application Publication No. 2000-112078 (page 34, left column, line 42 to page 35, left column, line 2). Furthermore, in the thermal developing photosensitive material, the methods described in Japanese Patent Application Publication No. 2001-255617 (page 31, right column, line 46 to page 32, left column, line 17), etc., can be employed.

[0339] One example of the silver halide photographic photosensitive material involved in this invention is a photosensitive thermal developing photographic material. This technology is described in paragraphs 16 to 189 of Japanese Patent No. 5623921. In this method, when the surfactant in paragraphs 181 to 183 of that publication is the surfactant described in this application, the desired effect can be obtained.

[0340] (Diffusion transfer type silver halide photographic material)

[0341] The diffusion transfer type silver halide photographic material of the present invention has a support and a layer disposed on the support, comprising an ionic compound having an anionic structure represented by the following formula 1 (the ionic compound of the present invention).

[0342] [Chemical Formula 20]

[0343] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

[0344] The preferred embodiment of the ionic compound in the diffusion transfer type silver halide photographic material of the present invention is the same as the preferred embodiment of the ionic compound of the present invention described above.

[0345] In the diffusion transfer type silver halide photographic photosensitive material involved in this invention, the ionic compound involved in this invention may contain one type alone, or two or more types.

[0346] The content of the ionic compound involved in the present invention in the above-mentioned layer of the diffusion transfer type silver halide photographic photosensitive material involved in the present invention can be appropriately selected according to its use. Relative to the total mass of the above-mentioned layer, it is preferably 0.0001% to 50% by mass, more preferably 0.001% to 20% by mass, and especially preferably 0.01% to 10% by mass.

[0347] The aforementioned layers can be any layer constituting the diffusion transfer type silver halide photographic photosensitive material described later. Preferably, it is a layer that forms a gas-liquid interface during coating, and more preferably, it is the outermost layer of the final laminated photosensitive material. Specifically, it can be an intermediate layer in a photosensitive film substrate, the outermost layer of the substrate, an intermediate layer in a photosensitive film, a protective layer, a temperature compensation layer in a cover sheet, etc. Among these, the outermost layer of the substrate in a photosensitive film substrate, the protective layer of the photosensitive film, and the temperature compensation layer in a cover sheet are particularly preferred.

[0348] Furthermore, in the diffusion transfer type silver halide photographic material involved in this invention, the layer containing the ionic compound involved in this invention can be one layer or two or more layers.

[0349] The aforementioned layer may contain various components found in diffusion-transfer silver halide photographic materials, as described later.

[0350] The diffusion transfer type silver halide photographic photosensitive material involved in the present invention preferably comprises a photosensitive film, a transparent cover sheet, and an alkali-treated composition spread therebetween.

[0351] [1] The alkali-treated composition contains body

[0352] The alkali-treated composition contains an ingredient that functions to spread uniformly on the exposed photographic film and develop the photosensitive layer, and also functions to completely shield the photosensitive layer from external light together with the back of a transparent support provided on the photographic film or a light-shielding layer in the photographic film. Therefore, the alkali-treated composition typically contains, in addition to alkali, thickener, light-shielding agent, and developer, a development promoter for adjusting development, a development inhibitor, and an antioxidant for preventing the deterioration of the developer.

[0353] (a) base

[0354] There are no particular limitations as long as the base can raise the pH of the liquid to above 12. Examples of bases include alkali metal hydroxides (such as sodium hydroxide, potassium hydroxide, and lithium hydroxide), alkali metal phosphates (such as potassium phosphate), guanidines, and quaternary ammonium hydroxides (such as tetramethylammonium hydroxide). Among these, potassium hydroxide and sodium hydroxide are preferred.

[0355] (b) Developer

[0356] A developer can be any developer that cross-oxidizes the pigment image-forming compound and does not substantially produce stains even when oxidized. Developers can be used alone, in combination with two or more, or as precursors. Examples of developers include aminophenols and pyrazolones. Pyrazolones are particularly preferred due to their low stain production. Specific examples of pyrazolones include 1-phenyl-3-pyrazolone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolone, 1-(3'-methyl-phenyl)-4-methyl-4-hydroxymethyl-3-pyrazolone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolone, and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolone. Developers can be incorporated into alkaline-treated compositions or added to appropriate layers of photographic film.

[0357] (c) Sunscreen

[0358] There are no particular limitations on the use of any material that has a light-blocking function as a light-blocking agent. Examples of light-blocking agents include carbon black and biodegradable dyes as described in U.S. Patent No. 4,615,966. Carbon black is preferred among these light-blocking agents. Carbon black is not limited to carbon black obtained by a specific manufacturing method, but can be carbon black obtained by any manufacturing method. Examples of carbon black manufacturing methods include the channel method described in Donnel Voet “Carbon Black” Marcel Dekker, Inc. (1976), as well as the thermal method and the furnace method.

[0359] When using carbon black as an opacifier, it is preferable to prepare an aqueous dispersion of carbon black beforehand. Aqueous dispersions of carbon black are widely used as black or opacifier materials in coatings, inks, cosmetics, and photographic materials. To prepare an aqueous dispersion of carbon black, carbon black is typically added to water containing a suitable dispersant. After coarse dispersion using a coarse disperser (e.g., a high-speed stirring disperser such as the dissolver described in Japanese Patent Application Publication No. 54-36045), the average particle size of the carbon black is set to approximately 10 μm to 100 μm. Then, the particle size is further reduced using a fine disperser (e.g., a sand mill, homogenizer, colloid mill, etc.). Through this process, an aqueous dispersion of carbon black with an average particle size of approximately 0.1 μm to 10 μm can be obtained. Furthermore, as described in Japanese Patent Application Publication No. 58-52362, an aqueous dispersion of carbon black can also be prepared by dispersing carbon black in an aqueous solution containing an organic solvent and then removing the organic solvent.

[0360] Preferred dispersants include those described in pages 255-257 and 501-539 of the "Comprehensive Data Collection on Dispersion Technology" (Published by the Business Development Center). An example of a commercially available dispersant is DEMOL N (trade name, manufactured by Kao Corporation).

[0361] The type and / or amount of dispersant affects the sodium ion content described later. The type and / or amount of dispersant must satisfy not only (a) the condition of imparting sufficient dispersibility to the opacifier, but also (b) the condition of sodium ion content. To simultaneously satisfy both the dispersibility and sodium ion content conditions, it is preferable to set the amount of dispersant relative to the opacifier to 2% to 100% by mass.

[0362] (d) Optical Concentration

[0363] The optical concentration of the substance contained in the alkali-treated composition is preferably 47 or higher, more preferably 50 or higher, and particularly preferably 55 or higher. Sufficient light-blocking properties are obtained when the optical concentration is 47 or higher, and spotting haze can be suppressed. The amount of the light-blocking agent is preferably determined so that the optical concentration is 47 or higher. Although it also depends on the type of light-blocking agent used, it is preferable to set the amount of the light-blocking agent to approximately 10% to 40% by mass in order to achieve an optical concentration of 47 or higher.

[0364] (e) Sodium ion content

[0365] The sodium ion content of the alkali-treated composition is preferably 0.4 g / m³ in the developed state. 2 The sodium ion content is further preferably 0.35 g / m³. 2 The following is particularly preferred: 0.25 g / m 2 the following.

[0366] The sodium ion content is mainly determined by the dispersant and thickener in the aforementioned opaque agents.

[0367] Sodium carboxymethyl cellulose is particularly preferred as a thickener. Sodium carboxymethyl cellulose possesses sufficient spreading properties and stability. Using polyvinyl alcohol, hydroxyethyl cellulose, or alkali metal salts of carboxymethyl cellulose (excluding sodium) as thickeners can reduce the sodium ion content. However, these do not possess sufficient spreading properties and stability, and are therefore unsuitable for use alone. Therefore, it is preferable to primarily use sodium carboxymethyl cellulose as a thickener, while simultaneously using polyvinyl alcohol, hydroxyethyl cellulose, or alkali metal salts of carboxymethyl cellulose (excluding sodium).

[0368] Preferably, the sodium ion content in the developed state is 0.4 g / m³. 2 The degree of etherification and the amount of sodium carboxymethyl cellulose added are adjusted in the following manner. The degree of etherification of sodium carboxymethyl cellulose is preferably 0.5–2.7, more preferably 1.0–2.4. The amount of sodium carboxymethyl cellulose added is preferably 1%–15% by mass, more preferably 2%–10% by mass.

[0369] The alkali-treated composition containing the above-mentioned optical concentration and sodium ion content exhibits excellent light-blocking properties and pigment transfer properties even when thinly spread on a photographic film. In this specification, "thinly spread" means that the alkali-treated composition containing the composition is spread on the photographic film with a thickness of 10 μm to 80 μm. A preferred spreading thickness is 10 μm to 70 μm, and a more preferred spreading thickness is 20 μm to 60 μm.

[0370] [2] Photographic film

[0371] (a) First transparent support

[0372] The support for the photosensitive film can be any support commonly used in photographic photosensitive materials. The support for an integrated color diffusion transfer film unit needs to be transparent. The support is preferably smooth. Examples of support materials include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. To prevent light conduction, the support preferably contains trace amounts of dye or pigments such as titanium dioxide. The thickness of the photosensitive film support is preferably 25 μm to 350 μm, more preferably 50 μm to 210 μm, and particularly preferably 70 μm to 150 μm. A base coating (lead coating) is preferably provided on the surface of the support. Furthermore, if necessary, a layer to maintain curl balance or an oxygen barrier layer can be provided on the back side of the support. Regarding the oxygen barrier layer, reference can be made to the description in Japanese Patent Application Publication No. 56-78833.

[0373] (b) Image receiving layer

[0374] The image-receiving layer (dye-receiving layer) of the photographic film preferably contains a mordant and a hydrophilic colloid. The image-receiving layer can be a single layer or a structure composed of layers with different mordant strengths. For information on single-layer and multi-layer image-receiving layers, please refer to the description in Japanese Patent Application Publication No. 61-252551.

[0375] Polymer mordants are preferred as mordants. Polymer mordants refer to polymers containing secondary and / or tertiary amines, polymers having nitrogen-containing heterocyclic moieties, and polymers containing quaternary cations, etc., preferably polymers with a molecular weight of 5,000 or more, and particularly preferably polymers with a molecular weight of 10,000 or more. The coating amount of the mordant is preferably 0.5 g / m². 2 ~10g / m 2 More preferably 1g / m 2 ~5g / m 2 Especially preferred is 2g / m 2 ~4g / m 2 .

[0376] Examples of hydrophilic colloids include gelatin, polyvinyl alcohol, polyacrylamide, and polyvinylpyrrolidone. Gelatin is the preferred hydrophilic colloid.

[0377] The receiving layer may contain an anti-fading agent. There are no particular restrictions on the anti-fading agent; for example, the anti-fading agents described in Japanese Patent Application Publication Nos. 62-30620, 62-30621, and 62-215272 may be used.

[0378] The thickness of the receiving layer can be the same as that of the receiving layer in a typical color diffusion transfer film unit.

[0379] (c) White reflective layer

[0380] The white reflective layer of the photographic film forms the white background of the color image. The white reflective layer typically contains white pigment and a hydrophilic binder.

[0381] The whiteness of the white reflective layer is determined by the type of pigment, the mixing ratio of the pigment and the binder, and the amount of pigment applied. When the white pigment is titanium dioxide, the preferred titanium dioxide content is 5 g / m². 2 ~40g / m 2 More preferably 10g / m 2 ~25g / m 2 .

[0382] The light reflectivity of the white reflective layer is preferably 70% or more, and more preferably 78% to 85% for light with a wavelength of 540 nm.

[0383] Examples of white pigments include barium sulfate, zinc oxide, barium stearate, silver flakes, silicates, alumina, zirconium oxide, sodium zirconium sulfate, kaolin, mica, and titanium dioxide. Furthermore, non-film-forming polymer particles such as polystyrene can also be used as white pigments. Among these, titanium dioxide is preferred, and rutile titanium dioxide is particularly preferred. White pigments can be used alone or in combination with two or more other pigments. Using two or more white pigments makes it easier to set the reflectivity of the white reflective layer to an optimal value.

[0384] The preferred white pigment is one that has undergone surface treatment with alumina, silica, zinc oxide, or the like, and more preferably a white pigment with a surface treatment content of 5% or more. The white reflective layer containing the surface-treated white pigment exhibits high reflectivity.

[0385] Examples of commercially available titanium dioxide include DuPont's Ti-pure R931 (trade name) or the titanium dioxide described in Research Disclosure (RD) No. 15162.

[0386] Examples of hydrophilic adhesives include alkali-permeable polymer matrices such as gelatin and polyvinyl alcohol, or cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose. When gelatin is used as the adhesive, the mass ratio of white pigment to gelatin is preferably 1 / 1 to 20 / 1, more preferably 5 / 1 to 10 / 1.

[0387] The white reflective layer preferably contains an anti-fading agent. There are no particular restrictions on the anti-fading agent; for example, the anti-fading agents described in Japanese Patent Publication No. 62-30620 or Japanese Patent Publication No. 62-30621 may be used.

[0388] (d) Light-shielding layer

[0389] A light-shielding layer is disposed between the white reflective layer and the photosensitive layer. The light-shielding layer preferably contains a light-shielding agent and a hydrophilic adhesive.

[0390] The opaque agent can be the opaque agent described in (c) of the alkaline-treated composition described above. The content of the opaque agent varies depending on the photosensitivity of the photosensitive material to be opaque, but is generally preferably about 5 to 10 in terms of optical concentration.

[0391] The adhesive for the light-shielding layer can be any adhesive as long as it can disperse light-shielding agents such as carbon black. Gelatin is a preferred adhesive.

[0392] There are no particular restrictions on the thickness of the light-blocking layer, as long as it provides sufficient light-blocking capability without making the photosensitive film too thick.

[0393] (e) Photosensitive layer

[0394] The photosensitive layer is preferably adjacent to the light-shielding layer and contains a pigment image-forming compound and a silver halide emulsion. The photosensitive layer can be a multilayer formed of a silver halide emulsion layer and a pigment image-forming compound layer, or it can be a single layer containing both a silver halide emulsion and a pigment image-forming compound. The following description focuses on the multilayer case, but the same applies to the single-layer case.

[0395] (f) Pigment image forming compounds

[0396] Pigment image-forming compounds include yellow pigment-forming compounds, magenta pigment-forming compounds, and cyan pigment-forming compounds.

[0397] Specific examples of yellow pigment-forming compounds are described in U.S. Patent Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609, 4,139,383, 4,195,992, 4,148,641, 4,148,643, and 4,336,322; Japanese Patent Application Publication Nos. 51-114930, 56-71072, Research Disclosure Nos. 17630 (1978) and 16475 (1977).

[0398] Specific examples of magenta pigment-forming compounds are described in U.S. Patent Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, 3,954,476, 4,233,237, 4,255,509, 4,250,246, and 4,142,891, and in the United States. The patents described in Japanese Patent No. 4,207,104, US Patent No. 4,287,292, Japanese Unexamined Patent Publication No. 52-106727, Japanese Unexamined Patent Publication No. 53-23628, Japanese Unexamined Patent Publication No. 55-36804, Japanese Unexamined Patent Publication No. 56-73057, Japanese Unexamined Patent Publication No. 56-71060, Japanese Unexamined Patent Publication No. 55-134, Japanese Unexamined Patent Publication No. 7-120901, Japanese Unexamined Patent Publication No. 8-286343, Japanese Unexamined Patent Publication No. 8-286344, and Japanese Unexamined Patent Publication No. 8-292537 are mentioned.

[0399] Specific examples of blue pigment-forming compounds are described in U.S. Patent Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220, 4,242,435, 4,142,891, 4,195,994, and 4,147,544. The patents are cited in the following publications: U.S. Patent No. 4,148,642, British Patent No. 1,551,138, Japanese Patent Application Publication No. 54-99431, Japanese Patent Application Publication No. 52-8827, Japanese Patent Application Publication No. 53-47823, Japanese Patent Application Publication No. 53-143323, Japanese Patent Application Publication No. 54-99431, Japanese Patent Application Publication No. 56-71061, European Patent (EP) No. 53,037, European Patent (EP) No. 53,040, Research Disclosure No. 17,630 (1978), and Research Disclosure No. 16,475 (1977).

[0400] Pigment image forming compounds that form pigments through coupling can also be used as pigment image forming compounds. Examples of pigment image forming compounds that form pigments through coupling are described in Japanese Patent Application Publication Nos. 8-286340, 9-152705, 10-186564, and 10-293388.

[0401] Positive pigment image-forming compounds can also be used. Examples of positive pigment image-forming compounds are described in Japanese Patent Application Publication Nos. 4-156542, 4-155332, 4-172344, 4-172450, 4-318844, 4-356046, 5-45824, 5-45825, 5-53279, 5-107710, 5-241302, 5-107708, 5-232659, and U.S. Patent No. 5,192,649. Positive pigment image-forming compounds are preferably used in combination with negative silver halide emulsions, as described later.

[0402] Positive pigment image-forming compounds can be dispersed by the method described in Japanese Patent Application Publication No. 62-215272, pages 144-146. Furthermore, the dispersion may contain compounds described in Japanese Patent Application Publication No. 62-215272, pages 137-144. Specific examples of these pigment image-forming compounds include the following compounds. Additionally, in the following compounds, "Dye" represents a pigment group, a temporarily shortened pigment group, or a pigment precursor group.

[0403] [Chemical Formula 21]

[0404] [Chemical Formula 22]

[0405] [Chemical Formula 23]

[0406] (g) Silver halide emulsion

[0407] Silver halide emulsions can be negative silver halide emulsions that primarily form latent images on the surface of silver halide particles, or internal latent-image direct positive silver halide emulsions that form latent images inside the silver halide particles. Examples of internal latent-image direct positive silver halide emulsions include so-called "conversion emulsions" made by utilizing the poor solubility of silver halide, or "core / shell emulsions" formed by covering at least the photosensitive sites of the internal core particles of silver halide particles with the outer shell of silver halide, or by chemical sensitization or both. These are described in U.S. Patent No. 2,592,250, U.S. Patent No. 3,206,313, and British Patent No. 1,027,146. The specifications in U.S. Patent No. 3,761,276, U.S. Patent No. 3,935,014, U.S. Patent No. 3,447,927, U.S. Patent No. 2,297,875, U.S. Patent No. 2,563,785, U.S. Patent No. 3,551,662, U.S. Patent No. 4,395,478, German Patent No. 2,728,108, and various specifications in U.S. Patent No. 4,431,730, etc.

[0408] Furthermore, when using internal latent-image direct positive silver halide emulsions, it is necessary to use photo- or nucleating agents after image exposure to impart surface haze nuclei. As nucleating agents, hydrazines described in U.S. Patent No. 2,563,785, U.S. Patent No. 2,588,982, hydrazines and hydrazones described in U.S. Patent No. 3,227,552, British Patent No. 1,283,835, Japanese Patent Application Publication No. 52-69613, U.S. Patent Nos. 3,615,615, 3,719,494, 3,734,738, 4,094,683, and 4,115,122, heterocyclic quaternary salt compounds, and compounds with nucleating effects in pigment molecules as described in U.S. Patent No. 3,718,470, are all suitable. Substituent-enhancing materials, US Patent No. 4,030,925, US Patent No. 4,031,127, US Patent No. 4,245,037, US Patent No. 4,255,511, US Patent No. 4,266,013, US Patent No. 4,276,364, and British Patent No. 2,012,443, as well as thiourea-bonded acylhydrazine compounds, US Patent No. 4,080,270, US Patent No. 4,278,748, and British Patent No. 2,011,391B, as acylhydrazine compounds bonded with heterocyclic groups (thioamide rings, triazole rings, tetrazolium rings, etc.) as adsorption groups, etc.

[0409] In order to reduce the sensitivity of the reversible negative image and increase the sensitivity of the reversible positive image, the metal complexes described in Japanese Patent Application Publication Nos. 2002-40607 and 2003-107616 are preferred.

[0410] Regarding the preferred manufacturing method for negative silver halide emulsions, the method described in Japanese Patent Application Publication No. 2006-113291 is preferred.

[0411] This material can be used in combination with silver halide emulsions to create a spectrally enhanced staining agent. Specific examples are described in Japanese Patent Application Publication Nos. 59-180550, 60-140335, RD17029, and U.S. Patent Nos. 1,846,300, 2,078,233, 2,089,129, 2,165,338, 2,231,658, 2,917,516, 3,352,857, 3,411,916, and 2,295,276. In the specifications of U.S. Patent Nos. 2,481,698, 2,688,545, 2,921,067, 3,282,933, 3,397,060, 3,660,103, 3,335,010, 3,352,680, 3,384,486, 3,623,881, 3,718,470, and 4,025,349, etc.

[0412] (h) Structure in photographic film

[0413] The photographic film preferably has at least three layers of silver halide emulsion with different color sensitivities and at least two layers of anti-color mixing layers located between the aforementioned silver halide emulsion layers and having a non-diffusive reducing agent.

[0414] To impart different colorimetric properties to at least three layers of silver halide emulsion, it is effective and preferred to use the aforementioned spectral enhancement materials with different absorption wavelength distributions.

[0415] When imparting different color sensitivities to silver halide emulsions, it is preferable that their spectral sensitivity distributions do not overlap as much as possible, but they do not need to be completely separated. In a silver halide emulsion layer with at least three layers, different color sensitivities can be considered to exist if the following relationship holds true in each layer: the sensitivity of a single emulsion layer at a specific wavelength is more than twice that of the other at least two silver halide emulsion layers. In the relationship of sensitivity among at least three silver halide emulsion layers, it is preferable that the sensitivity of a single emulsion layer at a specific wavelength is at least five times, more preferably at least ten times, that of the other at least two silver halide emulsion layers. There is no limitation on the specific wavelength used to establish these relationships; it can be any of the visible, ultraviolet, or infrared regions. However, the silver halide emulsions in the at least three layers are preferably selected from silver halide emulsions that are sensitive to any of the blue, green, red, and infrared light.

[0416] The emulsion and the pigment image-forming compound can be configured as separate layers, or they can be contained in a single layer. When the pigment image-forming compound is coated, and the emulsion in which it is combined has absorption in the spectral sensitivity region, separate layers are preferred.

[0417] The emulsion layer can be formed from emulsions with different photosensitivity. Furthermore, any layer can be present between the emulsion layer and the pigment image-forming compound layer. For example, if a layer containing the nucleation and development promoter described in Japanese Patent Application Publication No. 60-173541 or a partition layer described in Japanese Patent Application Publication No. 60-15267 is provided, the color image density can be improved; if a reflective layer is provided, the photosensitivity of the photographic film can be improved. The reflective layer is a layer containing a white pigment and a hydrophilic binder; preferably, the white pigment is titanium dioxide, and preferably, the hydrophilic binder is gelatin. The coating amount of titanium dioxide is preferably 0.1 g / m². 2 ~8g / m 2 More preferably 0.2 g / m 2 ~4g / m 2 Examples of reflective layers are described in Japanese Patent Application Publication No. 60-91354.

[0418] In the case of a multi-layered photosensitive layer, it is preferable to arrange the combination units of blue photosensitive emulsion, green photosensitive emulsion, and red photosensitive emulsion sequentially from the exposure side. Any layer can be set between the emulsion layer units as needed.

[0419] (i) Anti-mixing color layer

[0420] To prevent the development effect of one emulsion layer from adversely affecting other emulsion layers, it is preferable to have an anti-mixing layer containing a non-diffusive reducing agent located between the emulsion layers. Since at least one anti-mixing layer is required between each emulsion layer, the photographic film preferably has at least two anti-mixing layers.

[0421] As a non-diffusive reducing agent used in the anti-mixing color layer, a known compound can be preferred.

[0422] For example, high molecular weight redox compounds described in Japanese Patent Application Publication No. 5-333501, phenanthrene ketones or hydrazine compounds described in International Patent Publication No. 98 / 33760, US Patent No. 4,923,787, and redox compounds described in German Patent Application Publication No. 19618786A1, European Patent Application Publication No. 839623A1, European Patent Application Publication No. 842975A1, German Patent Application Publication No. 19806846A1, and French Patent Application Publication No. 2760460A1 are also preferred. Furthermore, lactones described in Japanese Patent Application Publication No. 2000-122243 are also preferred.

[0423] The non-diffusive reducing agent used in the anti-mixing layer is preferably selected from non-diffusive hydroquinone derivatives, sulfonamide phenol derivatives, sulfonamide naphthol derivatives, and lactones. Non-diffusive hydroquinone derivatives are particularly preferred, among which dialkyl hydroquinone derivatives are preferred. Here, alkyl groups include substituted or unsubstituted alkyl groups, and substituents are not particularly limited as long as they do not impede the "non-diffusiveness" of the compound. Specific examples include aryl, acyl, alkoxycarbonyl, and aryloxycarbonyl groups. Furthermore, the total number of carbon atoms in the "dialkyl" group is preferably 12 or more, more preferably 16 or more.

[0424] The molecular weight of the non-diffusing reducing agent is preferably 350 or more, more preferably 390 or more, and particularly preferably 500 or more. When the anti-mixing agent is a polymer, the molecular weight is expressed as the number average molecular weight. The upper limit of the molecular weight of the non-diffusing reducing agent is not particularly limited when the non-diffusing reducing agent is a polymer, but when it is a compound other than a polymer, it is preferably about 1,000 or less. The optimal amount of non-diffusing reducing agent contained in at least two anti-mixing layers disposed between each silver halide emulsion layer varies depending on the coating amount, shape, particle size, and target maximum color development concentration of the silver halide emulsion used. However, if the amount of non-diffusing reducing agent is too large, it will lead to a decrease in color development concentration or a delay in image formation time; if it is too small, it will result in a cloudy color hue. Therefore, the amount of non-diffusing reducing agent should be set taking these factors into account. By setting a specific ratio of the coating amount of silver halide relative to these non-diffusing reducing agents, and by using a specific amount of negative silver halide emulsion as the silver halide emulsion, the decrease in color development concentration when the amount of silver coating is reduced can be effectively suppressed. The total molar number of silver halide coating is in the range of 5 to 10 times the total molar number of non-diffusive reducing agent used in the anti-miscoloration layer. The preferred total molar number of non-diffusive reducing agent is 0.5 mmol / m². 2 ~1.5mmol / m 2 Within the range, more preferably within 0.8 mmol / m 2 ~1.2mmol / m 2Within the range.

[0425] The following are specific examples of non-diffusive reducing agents, but the present invention is not limited to these.

[0426] [Chemical Formula 24]

[0427] The non-diffusion reducing agent preferably exists in the anti-mixing layer in the form of tiny oil droplets obtained by dissolving in a high-boiling-point organic solvent and dispersing through emulsification. The high-boiling-point organic solvent is preferably a high-boiling-point organic solvent in the range of 4.0 to 8.0. The high-boiling-point organic solvent can be a mixture of two or more types. Examples of preferred high-boiling-point organic solvents include phthalates, phosphate esters, organic acid amides, ketones, etc. Here, the dielectric constant is measured using a transformer bridge method (TRS-10T manufactured by ANDO ELECTRIC CO., LTD.) at 25°C and 10 kHz. The boiling point of the high-boiling-point organic solvent is preferably 140°C or higher, and the melting point is preferably 100°C or lower, more preferably 160°C or higher and 70°C or lower. The high-boiling-point organic solvent can be a high-boiling-point organic solvent that is solid at room temperature, in which case the dielectric constant is a value measured in a liquid (supercooled state). The amount (mass ratio) of the high-boiling-point organic solvent in the anti-mixing layer relative to the non-diffusive reducing agent is preferably 0.3 to 20, more preferably 0.5 to 10, and even more preferably 1 to 8.

[0428] As long as sufficient color reproduction capability is achieved, and within the range that the thickness of the photosensitive layer is not excessive, there is no particular limitation on the thickness of the photosensitive layer.

[0429] (j) Other

[0430] Photosensitive films can have anti-light bleeding layers, UV absorption layers, protective layers, etc., as needed.

[0431] There are no particular restrictions on the thickness of the photosensitive film, as long as it does not make the color diffusion transfer film unit too thick.

[0432] [3] Transparent covering sheet

[0433] (a) Second transparent support

[0434] The support for the transparent cover sheet can be any smooth, transparent support commonly used in photographic photosensitive materials. Preferred supports include cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate. The support preferably contains a trace amount of dye to prevent light conduction. Furthermore, a base coating is preferably provided on the support.

[0435] (b) Layers with neutralizing function

[0436] The neutralizing layer (neutralizing layer) is a layer containing an amount of acidic substance sufficient to neutralize the alkali introduced from the alkali-treated composition. Depending on the requirements, it can be a multi-layered structure composed of layers such as a neutralization rate regulating layer (neutralization timing layer) and a sealing reinforcement layer.

[0437] Preferred acidic substances are those containing acidic groups with a pKa of 9 or less (or precursor groups that produce acidic groups with a pKa of 9 or less through hydrolysis). More preferred acidic substances are higher fatty acids such as oleic acid as described in U.S. Patent No. 2,983,606; polymers of acrylic acid, methacrylic acid, or maleic acid and their esters or anhydrides as disclosed in U.S. Patent No. 3,362,819; copolymers of acrylic acid and acrylates as disclosed in French Patent No. 2,290,699; and latex-type acidic polymers as disclosed in U.S. Patent No. 4,139,383 or RD No. 16102 (1977). In addition, acidic substances disclosed in U.S. Patent No. 4,088,493, Japanese Patent Application Publication No. 52-153739, Japanese Patent Application Publication No. 53-1023, Japanese Patent Application Publication No. 53-4540, Japanese Patent Application Publication No. 53-4541, and Japanese Patent Application Publication No. 53-4542 are also preferred.

[0438] Other examples of acid polymers include copolymers of vinyl monomers such as ethylene, vinyl acetate, and vinyl methyl ether with maleic anhydride, as well as their n-butyl esters, copolymers of butyl acrylate and acrylic acid, cellulose, and acetate / hydrogenated phthalates.

[0439] Acidic polymers can be mixed with hydrophilic polymers. Examples of hydrophilic polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including some saponified forms), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and polymethyl vinyl ether. Polyvinyl alcohol is preferred. Polymers other than hydrophilic polymers, such as cellulose acetate, can be mixed with the acidic polymer.

[0440] The coating amount of the acidic polymer is determined based on the amount of alkali contained in the alkali-treated composition. The equivalence ratio of acidic polymer to alkali per unit area is preferably 0.9 to 2.0. If the acidic polymer is too little, the hue of the transfer pigment will change, or stains will form on white areas. Too much will also cause hue changes or reduced lightfastness. A further preferred equivalence ratio is 1.0 to 1.3. Too much or too little mixed hydrophilic polymer will also reduce the quality of the photograph. The mass ratio of hydrophilic polymer to acidic polymer is preferably 0.01 to 10, more preferably 0.1 to 3.0.

[0441] Additives can be added to the neutralizing layer for various purposes. For example, conventional film-forming agents can be added to strengthen the neutralizing layer, while polyhydroxy compounds such as polyethylene glycol, polypropylene glycol, and glycerin can be added to improve the film's brittleness. Furthermore, antioxidants, fluorescent whitening agents, development inhibitors, and their precursors can be added as needed.

[0442] In neutralization timing layers used in combination with neutralization layers, useful materials include, for example, gelatin, polyvinyl alcohol, partially acetalized polyvinyl alcohol, cellulose acetate, partially hydrolyzed polyvinyl acetate, and other polymers that reduce alkali permeability; latex polymers that have a small amount of hydrophilic comonomers such as acrylic acid monomers that increase alkali permeability; and polymers with lactone rings.

[0443] Of particular interest are the timed layers using cellulose acetate disclosed in Japanese Patent Application Publication No. 54-136328, U.S. Patent No. 4,267,262, U.S. Patent No. 4,009,030, and U.S. Patent No. 4,029,849; Japanese Patent Application Publication No. 54-128335, Japanese Patent Application Publication No. 56-69629, Japanese Patent Application Publication No. 57-6843, U.S. Patent No. 4,056,394, U.S. Patent No. 4,061,496, U.S. Patent No. 4,199,362, U.S. Patent No. 4,250,243, and U.S. Patent No. 4,256,827; and U.S. Patent No. 4,256,827. Latex polymers copolymerized with hydrophilic comonomers such as acrylic acid, as disclosed in specification No. 4,268,604, etc.; polymers containing polyols of monoacrylate or monomethacrylate, as disclosed in Japanese Patent Application Publication No. 11-2890; polymers containing lactone rings, as disclosed in US Patent No. 4,229,516; and other polymers disclosed in Japanese Patent Application Publication No. 56-25735, Japanese Patent Application Publication No. 56-97346, Japanese Patent Application Publication No. 57-6842, European Patent Application Publication No. 31,957A1, European Patent Application Publication No. 37,724A1, European Patent Application Publication No. 48,412A1, etc.

[0444] In addition, the substances described in the following documents can also be used.

[0445] Specifications in U.S. Patent No. 3,421,893, U.S. Patent No. 3,455,686, U.S. Patent No. 3,575,701, U.S. Patent No. 3,778,265, U.S. Patent No. 3,785,815, U.S. Patent No. 3,847,615, U.S. Patent No. 4,088,493, U.S. Patent No. 4,123,275, U.S. Patent No. 4,148,653, U.S. Patent No. 4,201,587, U.S. Patent No. 4,288,523, U.S. Patent No. 4,297,431, German Patent Application Publication (OLS) No. 1,622,936, German Patent Application Publication No. 2,162,277, RD15162, No. 151 (1976), etc.

[0446] The neutralization timing layer may contain developer inhibitors and / or their precursors disclosed in U.S. Patent No. 4,009,029, German Patent Application (OLS) No. 2,913,164, German Patent Application Publication No. 3,014,672, Japanese Patent Application Publication No. 54-155837, and Japanese Patent Application Publication No. 55-138745, hydroquinone precursors disclosed in U.S. Patent No. 4,201,578, other photographic additives or their precursors, etc. Furthermore, if an auxiliary neutralization layer as described in Japanese Patent Application Publication Nos. 63-168648 and 63-168649 is provided, it is effective in reducing changes in transfer concentration over time after treatment.

[0447] The neutralization timing layer can contain multiple of these materials. Multiple materials can be contained in one layer or in multiple separate layers.

[0448] (c) Other layers

[0449] In addition to the neutralizing layer, transparent cover sheets can also have auxiliary layers such as a backing layer, a protective layer, and a color-filtering dye layer.

[0450] The backing layer is provided to adjust curling or to provide slipability. The backing layer may contain light-filtering dyes. The protective layer is mainly used to prevent adhesion to the back of the cover sheet and to prevent adhesion to the protective layer of the photosensitive material when the photosensitive material and the cover sheet are overlapped.

[0451] By incorporating dyes into the transparent cover sheet, the photosensitivity of the photosensitive layer can be adjusted. Filter dyes can be added to the support structure of the cover sheet or to layers with neutralizing functions, backing layers, protective layers, or capturing mordant layers. Furthermore, a separate layer of filter dyes can also be provided.

[0452] The diffusion transfer type silver halide photographic material involved in this invention can contain other known additives in each layer.

[0453] Example

[0454] The following examples illustrate the invention in further detail. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the invention is not limited to the specific examples shown below.

[0455] Furthermore, in this embodiment, unless otherwise stated, “%” and “parts” represent “mass %” and “mass parts”, respectively.

[0456] (Example S1)

[0457] <Synthesis of Intermediate 1>

[0458] [Chemical Formula 25]

[0459] 19.62 g of diallyl fumarate and 71.3 g of 2-propanol (iPrOH) were added to a 300 mL three-necked flask equipped with a stirrer, cooling pipe, nitrogen inlet pipe, and thermometer, and then replaced with nitrogen. 10.4 g of sodium bisulfite (NaHSO3) diluted with 24.7 g of deionized water was added, and the mixture was reacted in an oil bath at 90 °C for 6 hours.

[0460] After removing 2-propanol and water by vacuum distillation, 150 g of ethyl acetate was added and stirred. The precipitated solid was recovered by filtration. The obtained solid was dispersed and washed in 150 g of ethyl acetate for 1 hour, filtered, and dried to obtain 20.5 g of a white solid, intermediate 1. 1 H-NMR confirmed that the white solid was intermediate 1.

[0461] <Synthesis of Compound Al-1Na>

[0462] [Chemical Formula 26]

[0463] In a three-necked flask equipped with a stirrer, cooling tube, nitrogen inlet tube, and thermometer, 2.30 g (7.65 mmol) of intermediate 1, 162 mg (1.50 mmol) of 1,5-cyclooctadiene (cod) and 18 mL of methanol (MeOH) were weighed. After nitrogen purging, the mixture was stirred at 45 °C for 10 minutes. 201 mg (0.30 mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer ([IrCl(cod)]2) was added, and the mixture was stirred for another 10 minutes. Then, 3.34 g (15.0 mmol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added dropwise over 10 minutes. After the addition was complete, the reaction was carried out at 45 °C for 2 hours. 1 ¹H-NMR spectroscopy confirmed the complete disappearance of 1,1,1,3,5,5,5-heptamethyltrisiloxane, yielding the target compound Al-1Na. After removing methanol from the solvent by vacuum distillation, the compound was purified by silica gel column chromatography with ethyl acetate / methanol as the developing solvent, yielding 4.08 g (73% yield) of Al-1Na.

[0464] 1 H-NMR (MeOD): δ (ppm) = -0.11~0.12ppm (42H), 0.36~0.48ppm (4H), 1.50~1.66ppm (4H), 2.85~3.15ppm (4H), 3.52~4.08ppm (5H)

[0465] (Example S2)

[0466] <Synthesis of compound Al-2Na>

[0467] [Chemical Formula 27]

[0468] The amount of 1,1,3,5,5,5-heptamethyltrisiloxane 3.34 g was changed to 1,1,1,3,3,5,5-heptamethyltrisiloxane 3.34 g. Otherwise, compound A1-2Na was synthesized in the same manner as compound A1-1Na (yield 79%).

[0469] 1 H-NMR (MeOD): δ (ppm) = -0.10~0.10ppm (42H), 0.42~0.56ppm (4H), 1.54~1.70ppm (4H), 2.85~3.15ppm (4H), 3.90~4.10ppm (5H)

[0470] (Example S3)

[0471] <Synthesis of compound Al-3Na>

[0472] [Chemical Formula 28]

[0473] 3.34 g of 1,1,3,5,5,5-heptamethyltrisiloxane was replaced with 4.45 g of tris(trimethylsiloxy)silane, and the reaction was carried out at 60 °C for 6 hours. Otherwise, compound A1-3Na (yield 51%) was synthesized in the same manner as compound A1-1Na.

[0474] 1 H-NMR (MeOD): δ (ppm) = 0.02~0.20ppm (54H), 0.44~0.58ppm (4H), 1.60~1.80ppm (4H), 2.98~3.24ppm (4H), 3.96~4.22ppm (5H)

[0475] (Example S4)

[0476] <Synthesis of Intermediate 2 and Intermediate 3>

[0477] [Chemical Formula 29]

[0478] 499.0 g of ethyl acetate (AcOEt), 24.30 g of deionized water, and palladium / carbon (Pd / C, 5% palladium, approximately 55% water-wetting solution) were added to a 1000 mL three-necked flask equipped with a stirrer, cooling tube, nitrogen inlet tube, and thermometer, and then replaced with nitrogen. The flask was placed in an ice bath, and 100.0 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added dropwise over 30 minutes. After the addition was complete, the mixture was allowed to return to room temperature and reacted for 3 hours. Following the reaction, the palladium / carbon was removed by diatomaceous earth filtration, and the mixture was concentrated under reduced pressure using a rotary evaporator to obtain 100.5 g of a colorless, transparent liquid. 1 H-NMR confirmed that the liquid was intermediate 2.

[0479] Next, 99.0 g of the obtained intermediate and 285 g of toluene were added to a 500 mL three-necked flask equipped with a stirrer, cooling tube, nitrogen inlet tube, and thermometer. The flask was then immersed in an ice bath. Once the temperature was confirmed to be below 5°C, 32.5 g of pyridine was added dropwise, and stirring continued until the temperature returned to below 5°C. In a dropping funnel, 18.4 g of toluene and 19.3 mL of dichloromethylsilane were added and mixed to prepare a solution. This prepared solution was added dropwise to the three-necked flask over 30 minutes. After the addition was complete, the reaction mixture was brought to room temperature and allowed to react for 3 hours. After the reaction, the precipitated solid was filtered off, and the resulting colorless, transparent liquid was separated. The organic layer was recovered by two separations using 350 mL of ion-exchanged water. Magnesium sulfate was added to the organic layer, and after dehydration for at least 30 minutes, the liquid was concentrated under reduced pressure using a rotary evaporator. The obtained liquid was mixed with pulverized silica gel (Wakogel C-200 manufactured by FUJIFILMWako Pure Chemical Corporation), stirred, and then filtered by suction to obtain a colorless and transparent liquid. 1 H-NMR confirmed that the liquid was intermediate 3.

[0480] <Synthesis of compound Al-4Na>

[0481] [Chemical Formula 30]

[0482] 3.34 g of 1,1,3,5,5,5-heptamethyltrisiloxane was replaced with intermediate 3 (7.79 g), and otherwise, compound A1-4Na was synthesized in the same manner as compound A1-1Na (yield 74%).

[0483] 1 H-NMR (MeOD): δ (ppm) = -0.12~0.10ppm (90H), 0.42~0.56ppm (4H), 1.54~1.70ppm (4H), 2.85~3.15ppm (4H), 3.84~4.12ppm (5H)

[0484] (Examples 1-A to 1-D and Comparative Examples 1-A to 1-C: Evaluation of surface tension in aqueous solutions)

[0485] A sample for surface tension measurement was prepared by mixing 0.4 parts by mass of the synthesized compound or comparative compound, 1,000 parts by mass of ion-exchanged water, and 10 parts by mass of methanol. The prepared sample was kept at 40°C, and the surface tension was measured using the Wilhelmy method with a platinum plate as a probe, employing an automated surface tension meter DY-300 manufactured by Kyowa Interface Science Co., Ltd.

[0486] The measurement results are shown in Table 2.

[0487] [Table 2]

[0488] The following shows the comparative compounds C-1 and C-2 listed in Table 2.

[0489] [Chemical Formula 31]

[0490] (Examples 2-A to 2-H and Comparative Examples 2-A to 2-C: Preparation of compositions for image receiving films, fabrication of films and evaluation)

[0491] As a substrate for the sixth layer coating liquid, a composition (PA) containing the components shown in Table 3 was prepared relative to 1,000 g of the completed coating liquid. The remaining component in the composition (PA) is water.

[0492] [Table 3]

[0493] Furthermore, the composition (PA) described in Table 3 has a gelatin coating amount of 0.29 g / m³. 2 The coating was applied in a specific manner.

[0494] In addition, a substrate was prepared by laminating a back layer on a polyethylene terephthalate support, followed by laminating a substrate-first layer and a substrate-second layer. On this substrate, four layers—substrate-third to substrate-six—were simultaneously extruded from a die onto a sliding surface at a coating speed of 60 m / min. The coated image-receiving film was then stored at 25°C and 55% relative humidity for 7 days to harden. The sample thus obtained was used as image-receiving film substrate 101.

[0495] The composition of each layer is shown in Table 4 below.

[0496] Furthermore, to rigorously evaluate the stability of cratering during coating, coarse particles with a diameter of 6 μm were intentionally added to composition (A). The incorporation of foreign matter in the coating environment or the detachment of foreign matter from the backing layer can be causes of cratering during coating. The coarse particles were added for simulation purposes.

[0497] [Table 4]

[0498] Compositions (PB) to (PK) with only the type of compound changed were prepared for the composition (PA) used as the substrate-6th layer coating liquid. Details are shown in Table 5 below. Furthermore, for the image receiving thin film substrate 101, image receiving thin film substrates 102 to 111 were prepared in the same manner, except that the type of substrate-6th layer coating liquid was changed.

[0499] The obtained samples were evaluated as follows.

[0500] Evaluation 1) Coating surface appearance

[0501] -Evaluation of resistance to shrinkage cavities-

[0502] Observe 10m with the naked eye 2 The frequency of pinhole formation was evaluated on the coated samples.

[0503] The frequency of pinhole formation in each sample was evaluated as a fraction of 100 relative to the number of pinholes in the image receiving thin film substrate (silver halide photographic material) 101.

[0504] The evaluation results are shown in Table 5.

[0505] [Table 5]

[0506] The following shows the details of each component recorded by the abbreviations used in Tables 3 to 5 other than those mentioned above.

[0507] Surfactant (1): The following compounds

[0508] [Chemical Formula 32]

[0509] Surfactant (3): The following compounds

[0510] [Chemical Formula 33]

[0511] Surfactant (6): The following compounds

[0512] [Chemical Formula 34]

[0513] Surfactant (7): The following compounds

[0514] [Chemical Formula 35]

[0515] Additive (1): The following compounds

[0516] [Chemical Formula 36]

[0517] Additive (5): The following compounds

[0518] [Chemical Formula 37]

[0519] Additive (8): Carboxymethyl cellulose (CMC CELLOGEN 6A manufactured by DKS Co. Ltd.)

[0520] Additive (10): The following compounds

[0521] [Chemical Formula 38]

[0522] Additive (12): The following compounds

[0523] [Chemical Formula 39]

[0524] Additives (18): The following compounds

[0525] [Chemical Formula 40]

[0526] Matting agent (1): Polymethyl methacrylate spherical latex (average particle size 3μm)

[0527] Matting agent (2): Polymethyl methacrylate spherical latex (average particle size 6μm)

[0528] Hardening agent (1): The following compounds

[0529] Hardening agent (2): The following compounds

[0530] Hardening agent (4): The following compounds

[0531] [Chemical Formula 41]

[0532] Polymer mordants (1): The following compounds

[0533] [Chemical Formula 42]

[0534] Ultraviolet absorber (2): The following compounds

[0535] Ultraviolet absorber (3): The following compounds

[0536] [Chemical Formula 43]

[0537] When a composition containing the ionic compounds involved in this invention is used to prepare a functional material (functional film), a functional film with excellent coating surface is obtained.

[0538] In the preparation of the above-mentioned film substrate samples, a composition in which the matting agent and the leveling agent introduced by the matting agent were removed from the composition formulation of the substrate-6th layer was prepared, and the same evaluation was performed. As a result, it was confirmed that in the samples using the ionic compound involved in the present invention, a substrate in which the formation of pinholes was suppressed could be formed.

[0539] (Examples 3-A to 3-D and Comparative Examples 3-A to 3-C: Preparation of the composition, fabrication and evaluation of silver halide photographic materials)

[0540] <Fabrication of Substrates for Photosensitive Materials>

[0541] As described in Table 3 of Examples 2-A to 2-H and Comparative Examples 2-A to 2-C above, a back layer was laminated on a polyethylene terephthalate support, followed by the lamination of the first to sixth layers, thereby obtaining a laminated substrate (Subs-1).

[0542] At this time, the composition of the substrate - the 6th layer in Comparative Example 2-A composition (A) used a composition that does not contain matting agent (2) and surfactant derived from matting agent (surfactant (3)). The laminate substrate (Subs-1) was stored for 7 days after coating at an ambient temperature of 25°C and a relative humidity of 55%RH.

[0543] <Production of Photosensitive Materials>

[0544] As a coating solution for the 18th layer of a silver halide photosensitive material, a composition (QA) containing the components shown in Table 6 was prepared relative to 1,000 g of the completed coating solution.

[0545] [Table 6]

[0546] Furthermore, the composition (QA) described in Table 6 above has a gelatin coating amount of 0.20 g / m³. 2 The coating was applied in a specific manner.

[0547] On a substrate (Subs-1) prepared as described above, layers 1 through 18 were simultaneously extruded from a die onto a smooth surface at a coating speed of 60 m / min. After coating, the photosensitive material was stored at 25°C and 55% RH for 7 days to promote the hardening reaction. The sample thus obtained was used as a comparative example of silver halide photographic photosensitive material 201.

[0548] The composition of each layer is shown in Tables 7 to 9.

[0549] Furthermore, to mandate evaluation of crater stability during coating, coarse particles with a diameter of 6 μm were intentionally added to the above composition (QA). By intentionally adding coarse particles with a very low frequency of mixing, crater evaluation can be performed over a narrow coating area.

[0550] [Table 7]

[0551] [Table 8]

[0552] [Table 9]

[0553] Furthermore, compositions (QB) to (QG) were prepared by changing the compound to that shown in Table 12 below, relative to composition (QA). Silver halide photographic materials 202 to 207 were prepared in the same manner as silver halide photographic materials 201, except that the type of coating liquid for the 18th layer was changed.

[0554] The obtained photosensitive material samples were evaluated as follows.

[0555] Evaluation) Coating surface

[0556] When evaluating the coating surface, two evaluations were conducted: one for pinholes and one for uniformity.

[0557] -Evaluation of shrinkage cavities-

[0558] Observe 10m with the naked eye 2 The frequency of pinhole formation was evaluated on the coated samples.

[0559] The frequency of pinhole formation in each sample was evaluated as a fraction of 100 relative to the number of pinholes in silver halide photosensitive material 201.

[0560] -Evaluation of uniformity-

[0561] When the coating liquid is extruded from the die head onto the sliding surface and applied to the support, an airflow of about 2 m / s is applied to the sliding surface to force the coating process, making the coating surface easily disordered.

[0562] The coated photosensitive material was uniformly exposed to achieve a gray concentration of approximately 0.7, followed by development. The image, measuring 10 cm in width and 1 m in length, was visually inspected to evaluate the uniformity of the coating. The evaluation primarily focused on streaky non-uniformity. The evaluation criteria are shown below.

[0563] A: Uneven levels caused by wind cannot be identified.

[0564] B: It is almost impossible to detect uneven levels caused by wind.

[0565] C: A level where unevenness caused by wind can be identified to some extent, but is not a problem in practical application.

[0566] D: Able to identify wind-induced striped unevenness; if the photographic image is a uniform gray, then the level is problematic.

[0567] E: Capable of identifying wind-induced striped unevenness, even in photographic images containing patterned unevenness, with a high level of accuracy.

[0568] Furthermore, the silver halide photographic material prepared above is a diffusion transfer type silver halide photographic material. Its processing method involves developing a thin layer of spreading solution between the exposed silver halide photographic material (photosensitive film) and a transparent cover sheet. The transparent cover sheet contains cellulose acetate and an acidic polymer. The mechanism is as follows: cellulose acetate is hydrolyzed by the alkali in the processing solution, increasing the alkali's permeability. The processing solution maintains a high pH for approximately 10 minutes to develop the silver in the photosensitive material. Then, neutralization is achieved by the acidic polymer, resulting in a rapid decrease in pH after approximately 15-20 minutes, stopping the development. The processing solution is filled into a pressure-breaking container, which is then broken with rollers to achieve a spreading thickness of 55 μm.

[0569] The composition of the transparent covering sheet is shown in Table 10, and the composition of the treatment liquid is shown in Table 11.

[0570] Furthermore, the evaluation results are shown in Table 12.

[0571] [Table 10]

[0572] [Table 11]

[0573] [Table 12]

[0574] The following shows the details of the components recorded by the abbreviations used in Tables 6 to 12 other than those mentioned above.

[0575] Ultraviolet absorber (1): The following compounds

[0576] [Chemical Formula 44]

[0577] Hardening agent (3): The following compounds

[0578] [Chemical Formula 45]

[0579] Hardening agent (5): The following compounds

[0580] [Chemical Formula 46]

[0581] Additive (2): The following compounds

[0582] [Chemical Formula 47]

[0583] Additive (3): The following compounds

[0584] Additive (4): The following compounds

[0585] Additives (6) to (8): The following compounds

[0586] Additive (9): Polyvinyl alcohol (PVA-220E manufactured by KURARAY CO., LTD., degree of polymerization approximately 2,000, degree of saponification 88%)

[0587] Additive (11): The following compounds

[0588] Additives (13): The following compounds

[0589] [Chemical Formula 48]

[0590] Additives (14): The following compounds

[0591] [Chemical Formula 49]

[0592] Additives (20): The following compounds

[0593] Additive (21): The following compounds

[0594] [Chemical Formula 50]

[0595] Additives (22): The following compounds

[0596] [Chemical Formula 51]

[0597] Additives (23): The following compounds

[0598] [Chemical Formula 52]

[0599] Nucleating agent (1): The following compounds

[0600] [Chemical Formula 53]

[0601] Surfactant (4): The following compounds

[0602] [Chemical Formula 54]

[0603] Surfactant (5): The following compounds

[0604] [Chemical Formula 55]

[0605] Compound (P-8): The following compound, Mw33,700

[0606] [Chemical Formula 56]

[0607] High-boiling-point organic solvents (1): the following compounds

[0608] High-boiling-point organic solvents (2): the following compounds

[0609] [Chemical Formula 57]

[0610] Yellow pigment-releasing compounds (1): The following compounds

[0611] Magenta pigment-releasing compound (1): The following compounds

[0612] Cyan pigment-releasing compounds (1): The following compounds

[0613] [Chemical Formula 58]

[0614] Cyan pigment releasing compound (2): The following compounds

[0615] [Chemical Formula 59]

[0616] Temperature-compensated polymer (1): The following compounds

[0617] Temperature-compensated polymer (2): The following compounds

[0618] [Chemical Formula 60]

[0619] Acidic polymer (1): The following compounds

[0620] [Chemical Formula 61]

[0621] Internally embedded direct imaging emulsions A to I: prepared according to the emulsion of sample 101 in Japanese Patent Application Publication No. 2002-40607. The fourth layer uses emulsion G prepared according to emulsion RM12 as described in paragraphs 0052-0053 and 0057-0061.

[0622] [Table 13]

[0623] [Table 14]

[0624] Infecting materials (1) to (9): the following compounds

[0625] [Chemical Formula 62]

[0626] [Chemical Formula 63]

[0627] [Chemical Formula 64]

[0628] As shown in Table 12, if a composition containing the ionic compound involved in this invention is used in the outermost coating liquid, a silver halide photographic material with excellent coating surface can be obtained.

[0629] (Example 4)

[0630] Composition (R) was prepared with a modified composition formulation for the substrate-6th layer used in the silver halide photographic material of Example 3-A. The substrate (Subs-1) with the functional layer was replaced with composition (R) using the composition for the 6th layer. Otherwise, a substrate (Subs-2) containing the ionic compound according to the present invention was prepared in the same manner.

[0631] The multilayer photosensitive material compositions used in Examples 3-A to 3-D (silver halide photographic photosensitive materials 204 to 207) were coated on the substrate and evaluated in the same way as in Example 3-A. The results showed that the samples containing the ionic compound of the present invention in both the substrate and the photosensitive material layered on top exhibited excellent coating surface properties.

[0632] [Table 15]

[0633] In addition, composition (R) is an aqueous composition, and the remaining component in composition (R) as described in Table 15 is water.

[0634] (Example 5: Thermally developable photosensitive material)

[0635] In sample 7 of the examples described in Japanese Patent Application Publication No. 2006-91780, a substitute for fluorine compound (F-29) was prepared by replacing it with 10.0 mg / m³. 2 The sample of compound Al-1Na.

[0636] Regarding the obtained sample, the reflected light was observed with the naked eye at a brightness of 500 lux, and the surface texture was observed according to the following evaluation criteria. The result was rated as A, indicating that the coating surface texture is excellent.

[0637] A: Uneven levels cannot be identified.

[0638] B: Uneven levels are almost impossible to detect.

[0639] C: Slightly confirm the level of decrease in surface gloss.

[0640] D: The level of surface gloss reduction is clearly confirmed.

[0641] (Example 6: Thermally developed photosensitive material)

[0642] In Example 1 described in Japanese Patent No. 6851389, the fluorinated surfactants F-1 and F-2 (totaling 1 part by mass) in the non-photosensitive back protective layer were replaced with compound Al-1Na (10 parts by mass). Furthermore, the fluorinated surfactants F-1 and F-2 (totaling 1 part by mass) in the second layer of the surface protective layer were replaced with compound Al-1Na (10 parts by mass). The prepared sample was evaluated for its surface finish according to the same criteria as in Example 5, and the evaluation result was A, indicating excellent coating surface finish.

[0643] (Example 7: Industrial X-ray photosensitive material)

[0644] In Example Sample No. 14 disclosed in Japanese Patent Application Publication No. 2009-86332, a sample was prepared in which coating aids-4 and-5 (totaling 1 part by mass) of the surface protective layer were replaced with compound Al-1Na (10 parts by mass). The surface finish of the obtained sample was evaluated according to the same criteria as in Example 5, and the evaluation result was A, indicating that the coating surface finish was excellent.

[0645] (Example 8: Thermal Recording Material)

[0646] In Comparative Example 4 as described in International Publication No. 2016 / 194915, the N-propyl-N-polyoxyethylene-perfluorooctanesulfonamide sodium butyl sulfonate and potassium perfluorooctane sulfonate (totaling 1 part by mass) in the BPC layer (back protective layer) were replaced with compound Al-1Na (10 parts by mass). Furthermore, the Surflon S231W (manufactured by SEIMI CHEMICAL CO.,LTD.) and Plysurf A217 (manufactured by DKS Co. Ltd.) in the protective layer (totaling 1 part by mass) were replaced with compound Al-1Na (10 parts by mass). The surface finish of the prepared sample was evaluated according to the same criteria as in Example 5, and the evaluation result was A, indicating excellent coating surface finish.

[0647] The invention of Japanese Patent Application No. 2024-043969, filed on March 19, 2024, is incorporated herein by reference in its entirety.

[0648] All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent that each document, patent application and technical standard specifically and individually described and incorporated by reference.

Claims

1. An ionic compound having an anionic structure represented by Formula 1 below, [Chemical Formula 1] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

2. The ionic compound according to claim 1, wherein it is a compound represented by formula 2. [Chemical Formula 2] In Equation 2, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom. M 1 Indicates cations with valences of 1 to 3. n represents the relationship with M 1 Integers from 1 to 3 with equal valence.

3. The ionic compound according to claim 1 or 2, wherein, The value of w is 1.

4. The ionic compound according to claim 1 or 2, wherein, The anion structure represented by Formula 1 is a structure represented by any one of Formula a-1, Formula a-2, or Formula a-3 below. [Chemical Formula 3] In equations a-1 to a-3, Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. L A Indicates a single bond or a divalent linkage group. b represents 1 or 2. R B Represents a hydrogen atom or a hydrocarbon group. L B Indicates a single bond or a divalent linkage group, with two or more L... B They can be the same or different. Lc1 represents a single bond or a divalent linkage group. Two or more Lc1 groups can be the same or different. Lc2 represents a single bond or a divalent linkage group.

5. The ionic compound according to claim 1 or 2, wherein, The Sil1 is a group represented by any one of the following formulas Si-1 to Si-4. [Chemical Formula 4] In formulas Si-1 to Si-4, R1 represents a hydrocarbon group; multiple R1 groups can be the same or different. y represents an integer greater than 2. R2 represents a hydrocarbon group; multiple R2 groups can be the same or different. z represents 2 or 3. R3 represents a hydrocarbon group; multiple R3 groups can be the same or different. p and q represent integers that satisfy p≥1, q≥1, and p+q≥3. R4, R 4a and R 4b Indicates a hydrocarbon group, multiple R4, R 4a and R 4b They can be the same or different. This indicates the bonding position with L1.

6. A composition comprising: Ionic compounds having an anionic structure represented by Formula 1 below; and Adhesive, [Chemical Formula 5] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

7. A functional material having: Support body; and The layer, on the support, comprises an ionic compound having an anionic structure represented by Formula 1 below. [Chemical Formula 6] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

8. A silver halide photographic photosensitive material, comprising: Support body; and The layer, on the support, comprises an ionic compound having an anionic structure represented by Formula 1 below. [Chemical Formula 7] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

9. A diffusion-transfer type silver halide photographic photosensitive material, which has the following characteristics: Support body; and The layer, on the support, comprises an ionic compound having an anionic structure represented by Formula 1 below. [Chemical Formula 8] In Equation 1, w represents an integer greater than or equal to 1. x represents an integer greater than or equal to 2. Sil1 indicates a substituent containing at least three Si atoms. Two or more Sil1 groups can be the same or different. L1 represents a divalent linker group; two or more L1 groups can be the same or different. R represents an (x+w) valence organic group containing a carbon atom.

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